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Encyclopedia of Inorganic Chemistry
Encyclopedia of Inorganic Chemistry
Encyclopedia of Inorganic Chemistry
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Element Date Discovering group(s) Synthesis quantities
Actinium (89) Ac 1899 A. Debierne Naturally occurring kg
derived from Greek word for ray
(akinos)
Thorium (90) Th 1828 J. J. Berzelius Naturally occurring kg
named after Thor, mythological
Norse god
Protactinium (91) Pa 1913 K. Fajans, O. Gorhing Naturally occurring kg
derived from Greek word for first O. Hanh, L. Meitner
(protos) F. Soddy, J. Cranston
Uranium (92) U 1789 M. H. Klaproth Naturally occurring kg
named after the planet uranus
Neptunium (93) Np 1940 E. M. McMillian, Bombardment of 238 1
92 U with 0 n kg
named after the planet neptune P. H. Abelson
Plutonium (94) Pu 1940 G. T. Seaborg, Bombardment of 238 2
92 U with 1 H kg
named after the planet pluto E. M. McMillian,
A. C. Wahl, J. Kennedy
Americium (95) Am 1944 G. T. Seaborg, R. A. James, Bombardment of 239 1
94 Pu with 0 n kg
named after America L. O. Morgan
Curium (96) Cm 1944 G. T. Seaborg, R. A. James, Bombardment of 239 4
94 Pu with 2 He g
named after P. and M. Curie L. O. Morgan, A. Ghiorso
Berkelium (97) Bk 1949 S. G. Thompson, A. Ghiorso, Bombardment of 241 4
95 Am with 2 He mg
named after University of G. T. Seaborg
California, Berkeley
Californium (98) Cf 1950 S. G. Thompson, K. Street, Bombardment of 242 4
96 Cm with 2 He g
named after the State and A. Ghiorso, G. T. Seaborg
University of California
Einsteinium (99) Es 1952 Argonne Natl Lab, Los Multiple neutron capture by 235
92 U g
named after A. Einstein Alamos Natl Lab, University in a thermonuclear explosion
of California
Fermium (100) Fm 1953 Argonne Natl Lab, Los Multiple neutron capture by 235
92 U g
named after E. Fermi Alamos Natl Lab, University in a thermonuclear explosion
of California
Mendelevium (101) Md 1955 A. Ghiorso, B. G. Harvey, Bombardment of 253 4
99 Es with 2 He atoms
named after D. Mendeleev G. R. Choppin,
S. G. Thompson,
G. T. Seaborg.
Nobelium (102) No 1957 1963 A. Ghiorso, T. Sikkeland, Bombardment of 243 15
95 Am with 7 He atoms
named after A. Nobel J. R. Walton, G. T. Seaborg
Lawrencium (103) Lr 1961 1965 A. Ghiorso, T. Sikkeland, Bombardment of 249
98
252
Cf with atoms
named after E. Lawrence A. E. Larsh, R. M. Latimer 10 11 243 18
5 B and 5 B or 95 Am with 8 O
One of the most common topics asked of those who It is interesting to note that with proper planning and limiting
work with the actinides relates to handling procedures. The the quantity of material that is handled in an experiment, the
radioactive nature of these elements does require the use overall annual radiation exposure for people working in a
of special facilities, processes, and precautions. However, synthetic or analytical radiological laboratory is less than that
working with radioactive elements in subcritical quantities is found for aircraft crew. In order to fully mitigate the risks
as safe, if not safer, than handling many of the toxic chemicals of handling radioactive material and maintain a minimum
found in a typical synthetic laboratory. The primary advantage radiation fields, it is important to have an understanding of the
in handling radioactive material is the ease with which these nuclear processes that are typically involved or could occur.
elements can be detected. Unlike other toxic chemicals, for An example of a common situation that leads to greater
example, lead, thallium, arsenic, and so on, a simple survey radiation exposure levels than would be expected occurs with
(seconds) with a radiation detector will show if containment some uranium compounds. Depleted uranium 238 U is an -
of the material has been lost, where it is, and approximately emitting isotope with an extremely long half-life, 4 billion
how much is present. With appropriate monitoring, virtually years. As a result of this long half-life, 238 U is generally not
no uptake of radioactive material occurs, and if any personnel considered to present a significant radiation hazard. However,
contamination does occur, it is quickly detected and treated. uranium fluorides, a typical synthetic starting material, can
ACTINIDES: INORGANIC & COORDINATION CHEMISTRY 3
Table 2 Half-lifes, mode of production, and decay mechanisms for the most widely used isotopes of the light actinides
Uranium ore is typically mined or leached in situ. For far the most commonly used physical method for enrichment
the mined ore, the raw material is milled to produce a high is gaseous diffusion.
surface area slurry, which is then treated with H2 SO4 . The Once enriched, the UF6 needs to be reduced to either
sulfuric acid oxidizes the uranium to the soluble hexavalent uranium metal or UO2 to be formed into fuel pins. A variety
state. The addition of base to the solution precipitates an oxide of methods can be used to accomplish the conversion to the
of uranium known as yellowcake, U3 O8 . A similar process oxide; however, the predominately used technique involves
is used for the in situ leaching of uranium ore except that the reduction of the UF6 to U metal fully, using Ca at high
initial treatment is performed on bores with a slightly acidic temperatures, followed by burning in oxygen. Once formed,
and high oxygenated aqueous solution that is raised to the the UO2 is pressed into pellets, which are then fed into
surface and allowed to go through an extraction process to fuel rods.
remove the uranium. The burning of the uranium-based nuclear fuel causes a
No matter which mining process is used, the final U3 O8 is cavalcade of chemical and physical transformations. Nuclear
converted to UF6 through a multistep process that takes the reactions lead to the formation of a variety of actinide
uranium through multiple species and oxidation states. In the elements, for example, Np, Pu, Am, and Cm, as radioactive
first step of the conversion process, the uranium is purified fission products. As a result of the production of these highly
by dissolving the yellowcake in nitric acid to produce the radioactive elements, burnt nuclear fuel must be allowed to
soluble uranyl ion, UO2 2+ , and purifying the aqueous stream cool until the short-lived isotopes decay away and reduce
through a solvent extraction process. The purified uranyl the thermal generation. The cooling typically takes place in
nitrate, UO2 (NO3 )2 6H2 O, is heated to produce uranium either water ponds or engineered dry casks/facilities.
trioxide, UO3 . The conversion of UO3 to UF6 is not an Once cooled, the fuel can be manipulated within hot
efficient process, so the oxide is reduced at high temperatures cell facilities for fuel reprocessing. In the United States, the
by H2 . The resulting UO2 is treated with HF to give UF4 , reprocessing of spent nuclear fuel has not been embraced.
commonly known as green salt. A reaction between UF4 The primary basis for this decision is the reduction of the
and gaseous F2 is the final step in the conversion process and threat of nuclear proliferation by avoiding the production of
yields nearly quantitatively gaseous UF6 . pure streams of plutonium. Some of the other concerns for
The purpose of going through the entire conversion process reprocessing are based in economics. Through the Advanced
is to obtain a uranium compound that can be run through a Fuel Cycle Initiative within the U.S. Department of Energy,
separations process to produce a product that is enriched in the technical feasibility of an economically, politically, and
235
U. Natural uranium is about 0.7% 235 U; however, electricity environmentally viable fuel cycle that includes recycling is
producing light water nuclear reactors require 3 to 5% 235 U. being investigated. Despite the US efforts, most of countries
The gaseous UF6 allows for multiple enrichment techniques to that have nuclear production capabilities use reprocessing.
be used, including gaseous diffusion, gaseous centrifugation, The chemistry of reprocessing is quite complex, but it
and laser techniques. The first two techniques rely on the mass embodies nearly every common aspect of inorganic chem-
differences between 235 U and 238 U to effect the separation. By istry: coordination, reduction/oxidation reactions, hard soft
ACTINIDES: INORGANIC & COORDINATION CHEMISTRY 5
acid base theory, and so on. The primary purpose of repro- metallic state within the weapons, the isotopic and chemical
cessing is to separate uranium and plutonium from the rest of purifications of these elements require complex separation
the actinides and fission products that are present in the spent chemistry and physics that are dependent on inorganic and
nuclear fuel. The method of choice to perform these separa- coordination compounds.
tions is liquid liquid extraction, for example PUREX process.
To effect the primary separation, the spent fuel is dissolved
in 7 M HNO3 . The resulting solution contains the uranyl ion, 2.3 Depleted Uranium Armor and Projectiles
UO2 2+ , and tetravalent plutonium cation, Pu4+ . This aqueous
Another military use of the actinide metals is in tank armor
solution is contacted with an organic solvent, for exam-
and armor piercing projectiles. Depleted uranium metal is an
ple kerosene, which contains tributylphosphate, OP(OBun )3
extremely dense material, for example, density of -phase
(TBP). The TBP molecule coordinates uranium and pluto-
U is 19 g cm3 , and is only mildly radioactive, half-life of
nium nitrate complexes and makes them soluble in the organic 238
U is 4.5 109 years. When this metal is incorporated into
phase. The molecules predominately attributed to this extrac-
a projectile, the density and metallic properties allow it to
tion are UO2 (NO3 )2 (TBP)2 and Pu(NO3 )4 (TBP)2 ; however,
penetrate deeply into heavily armored vehicles.
research continues to show that these simple formulations may
not accurately represent the speciation or the chemical envi-
ronment during the extraction. In order to separate the uranium 2.4 Heat Sources
and plutonium, a reducing agent, for example Fe(SO3 NH2 )2 ,
in an aqueous phase is contacted with the actinide-laden The portable generation or storage of power is essential
organic phase. The PuVI is reduced to PuIII , which does not to space exploration. In addition, maintaining working parts
form a strong complex and therefore selectively partitions to in the cold vacuum of space requires constant generation of
the aqueous phase. The uranium and plutonium can be purified heat. The electrical and heat requirements for a typical space
further and the respective oxides produced. The oxides are mission, for example, landing a rover on the surface of Mars,
then combined to produce a new nuclear fuel called mixed drive the need for extremely dense power sources. One of
oxide fuel (MOX ). the densest sources of energy is stored within the nucleus of
The remaining actinides and fission products must be radioactive materials. In order to tap into this energy source,
stabilized for interim storage, long-term storage or final space agencies have relied on plutonium in the form of the
disposal. In order to optimize the storage facilities, some -emitting 238 Pu isotope. The half-life for 238 Pu is 87 years,
additional separations of the remaining actinides and fission and when the dioxide is formed into pellets, it self-heats,
products are required. The European Union has been leading producing an orange glow. The following example can be
the course in the implementation of advanced separation used to emphasize the energy density of these materials: a
schemes, including diamide extraction (DIAMEX), selective 250-g (3 cm in diameter) 238 PuO2 ball acts as a 100-W heat
actinides extraction (SANEX) and SESAME. In DIAMEX, a source. The publicity of using these heat sources peaked in
diamide is used to separate the actinides and the lanthanides 1997 with the launch of the Cassini Huygens Mission to
from the fission products. In SANEX, a dithiophosphinic acid Saturn and Titan. The Cassini spacecraft was equipped with
is proposed to separate the actinides from the lanthanides. more than 200 238 PuO2 pellets (150 g each) within three
The reason this process works is the slightly higher degree radioisotope thermoelectric generators (RTGs). Each one of
of covalency that occurs in the bonding of the actinides these RTGs put out 4400 W of thermal energy at 1200 to
versus the lanthanides. In the SESAME process, americium 1300 C. Thermocouples are able to convert this thermal
and curium are separated using heteropolyanions, for example energy into 285 W of electricity. As for pure heat generation,
phosphotungstate P2 W17 O61 10 , that coordinate Am(IV) but the Cassini spacecraft and the Huygens probe use radioisotope
not Cm(III). heating units (RHUs). The RHUs are constructed with 2.7-g
The stabilization of the nuclear waste products is usually pellets of 238 PuO2 and maintain a temperature of 35 to 40 C.
performed by immobilizing the oxides of the radioactive
material in glass. This process is known as vitrification. The
environmental aspects of storing large quantities of radioactive 2.5 Smoke Detectors
glass logs are related to the leachability of the elements from
the glass structure.1,2 Americium plays a vital role in maintaining the safety
of homes across the world. The -emitting 241 Am isotope
can be found in most smoke detectors in the form of the
2.2 Nuclear Weapons dioxide, AmO2 . The -particle emission causes the air to
ionize between two electrodes. The ionization of the oxygen
Outside of nuclear energy, the most well-known utilization and nitrogen allows a steady current to flow between the
of the actinides is in nuclear weapons. The fissile nature electrodes. However, when smoke enters the detector, the -
of 235 U and 239 Pu has been exploited in the creation of particles are absorbed by the smoke and therefore ionize less of
nuclear arsenals throughout the world. Primarily found in the the air, which causes the current to drop and the alarm to signal.
6 ACTINIDES: INORGANIC & COORDINATION CHEMISTRY
Ac La
Th Ce
Pa Pr
U ? Nd
Np Pm
Pu ? Sm
fn
Am ? Eu
f0 f0
Cm ? ? f1 f1 Gd
f2 f2
Bk f3 f3 Tb
4 4
Cf f f ? Dy
f5 f5
Es f6 f6 Ho
Valence fn electronic
f7 f7
Fm configuration Er
f8 f8
9 9
Md f f Tm
f10 f10
No f11 f11 Yb
Lr f12 f12 Lu
f13 f13
f14 f14
been verified by a secondary source. The maximum possible the trivalent. However, when the making or a breaking of the
oxidation state can be reached for the elements from Ac An=O bond is required, for example, oxidizing the tetravalent
through Np. There has been a single report for the synthesis of to the pentavalent, the electrochemistry tends to be slow and
a PuVIII complex; however, this result has not been confirmed. irreversible.
In addition to being able to reach the maximum possible The structure and bonding within coordination complexes
oxidation state to get to a f 0 system, the most stable oxidation of the light actinides will be discussed in the following
state increases from Ac to U, AcIII , ThIV , PaV , and UVI . After section. However, the general trend between the actinides and
U, the most persistent oxidation state declines, for example, the lanthanides is a larger degree of covalency in An L bonds
NpV , PuIV , AmIII , until Cm, in which the trivalent ion continues versus Ln L bonds. In aqueous solutions, the predominant
to be the stable species. The only exception to this is No, where bonding interaction with ligands is ionic in character, and,
the divalent state predominates. therefore, the number and geometry of the ligands is mainly
determined by pure steric and electrostatic considerations. For
example, a wide range of coordination numbers (6 14) has
3.2 Chemical Characteristics been found for the actinide ions.
Table 3 Valence level electronic configuration of the actinides in the gas phase
Actinide Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm
Z 89 90 91 92 93 94 95 96 97 98 99 100
M (g) 6d 7s2 6d2 7s2 5f 2 6d 7s2 5f 3 6d 7s2 5f 4 6d 7s2 5f 6 7s2 5f 7 7s2 5f 7 6d 7s2 5f 9 7s2 5f10 7s2 5f11 7s2 5f12 7s2
M+ (g) 7s2 6d 7s2 5f 2 7s2 5f 3 7s2 5f 5 7s ? 5f 6 7s 5f 7 7s 5f 7 7s2 5f 9 7s 5f10 7s 5f11 7s2 5f12 7s
M2+ (g) 7s 5f 6d 5f 2 6d 5f 3 6d ? 5f 5 5f 6 5f 7 5f 8 5f 9 5f10 5f11 5f12
M3+ (g) 5f 5f 2 5f 3 5f 4 5f 5 5f 6 5f 7 5f 8 5f 9 5f10 5f11
M4+ (g) 5f 5f 2 5f 3 5f 4 5f 5 5f 6 5f 7 5f 8 5f 9 5f10
repulsion of the ligands. The actinide ions are relatively large important in the purification and processing of actinides, for
with the ionic radii for the An3+ and An4+ ions being 1.12 to example plutonium. Structure (10) represents the coordination
0.95 A and 0.94 to 0.82 A, respectively. As a result of their size, geometry for this anion, which has six bidentate nitrate ligands,
the actinides are found to have large coordination numbers, 6 giving the ion a coordination number of 12. The symmetry
to 14. Some examples of the typical coordination geometries for Structure (10) is Th with three sets of trans nitrato groups,
for the tri- and tetravalent actinide ions are shown in each making a plane in the Cartesian coordinate system.
structures (510). Structure (58) are the potential geometries The nonaqueous chemistry of the tri- and tetravalent ions
for the aquo ions, An(H2 O)8/9 3+/4+ . Structures (57) are eight- follows similar trends as the aqueous complexes. Coordination
coordinate with a cubic, square antiprism, and a bicapped numbers are dictated by the steric bulk and electronic
trigonal prism arrangement of the ligands, respectively. The properties of the ligands; two structures, U(MeBH3 )4 (11)
coordination number in Structure (8) is nine with a tricapped and [{U(N(CH2 CH2 NSiMe3 )3 )}2 (2 -2 : 2 -N2 )] (12), are
trigonal prismatic geometry. The higher coordination numbers shown. Direct comparisons of the latter species can be made
are observed with multidentate ligands, for example, CO3 2 to the behavior of transition metals in both coordination and
and NO3 . Structure (9) represents the An(CO3 )5 6 anion that reactivity.
has a coordination number of 10, resulting from five bidentate
carbonate ligands in an irregular geometry. The structure
can almost be compared with the high-valent linear dioxo Me
compounds with two trans carbonate ligands occupying the B SiMe3 Me3Si
SiMe3 SiMe3
axial sites and three nearly planar carbonate ligands occupying HHH N N
a pseudo-equatorial plane. The An(NO3 )6 2 anion is extremely H H Me N N N
B H U H B N U U N
Me H H
HH H N N N
3+/4+ 3+/4+
H2O OH2 H2O OH2 B SiMe3 Me3Si
H2O OH2 H2O OH2
Me
An An
H2O OH2 H2O OH2 (11) (12)
H2O OH2 H2O OH2
(5) (6)
For the high-valent aqueous actinide species, the predomi-
3+/4+ nant linear dioxo unit, AnO2 +/2+ , drives all of the coordination
3+/4+ H2O OH variability into the equatorial plane. It is interesting to note
H2O OH2 H2O 2
H2O OH2 H2O An
OH2 that the bonding for these ions have significant covalency
An OH2 with the axial An O ligands. However, for the majority of
H2O OH2 H2O
H2O OH2 the ligands residing in the equatorial plane (belly-band),
H2O OH2
the bonding is primarily ionic. This shows the dual behavior
(7) (8) (strong covalency and ionicity) of the trans dioxo ions. As a
result of this behavior, the linear dioxo unit is unperturbed
6
O O 2 (with the exception of bond distance changes) throughout all
of the aqueous-based complexes and the coordination num-
O OO O
O O bers are dictated by the equatorial ligands size and electronic
O O O O
O O O properties. The structures of a variety of aqueous-based coordi-
O An O O An O
O O nation complexes have been observed. Compounds with a D4h
O O O O O O
OO O O symmetry are represented by the complexes, AnO2 Cl4 2 (13)
and NpO4 (OH)2 3 (14). Seven-coordinate structures are also
O O
prevalent in actinide chemistry and are the highest coordina-
(9) (10) tion numbers achievable with all monodentate ligands. The
ACTINIDES: INORGANIC & COORDINATION CHEMISTRY 9
aquo ion (15) and pentafluoro (16) complex for the hexava- the electron has an inverse relationship with the Bohr radius,
lent actinides are represented below. Coordination complexes meaning as the mass increases the electron radius decreases.
under aqueous conditions with eight atoms bound to the There are two different relativistic effects, direct and indirect.
actinide are achievable. In general, direct relativistic effects are found for the s and p
orbitals, which contract owing to an increase in the mass of
these electrons. Indirect relativistic effects are predominantly
2 O 3
O found for the d and f orbitals, which generally have increased
Cl Cl HO O
An Np radii resulting from the enhanced shielding of the nuclear
Cl Cl O OH charge by the contracted s- and p-electrons. Understanding
O O
the difference between direct and indirect relativistic effects
(13) (14)
is actually a function of analyzing the angular wavefunctions
of the s, p, d, and f orbitals. The s- and p-electrons have a
2+ 3+
H2O O F
O greater probability of being found at the nucleus (minimal
OH2 F angular nodality) and, thus, greater probability of approaching
H2O An F An
OH2 F the speed of light. The diffuse nature of the d and f orbitals
H2O O F O
reduces the lifetime of the electrons close to the nucleus and,
(15) (16) therefore, the probability of being accelerated. Relativistic
effects increase as a function of the atomic number, Zn (n > 1),
and, therefore, actinides have greater relativistic effects
compared to the lanthanides. The effect can be recognized
4.3 Ionic Radii and the Actinide Contraction A Partial easily by looking at the calculated radial distribution functions
Relativistic Effect of Sm3+ and Pu3+ with and without relativistic effects. In
both ions, the s and p orbitals contract and the d and f orbitals
The ionic radii of the actinides is shown graphically in expand; however, the magnitude of the effect is clearly greater
Figure 2. The ionic radii for a given oxidation state gradually in the case of the Pu3+ ion.
decreases with increasing atomic number. This phenomenon
is known as the actinide contraction. Similar to the lanthanide
4.4 Molecular Orbital Descriptions The Linear Dioxo
contraction, the cause of the contraction is an increase in
Diagram
the effective nuclear charge experienced by the valence shell
electrons. The increase in the effective nuclear charge is Actinide complexes rarely follow the conventional rules,
a result of the additional protons and the poor shielding for example, 18-electron rule, typically found in inorganic
ability of the f-electrons due to their diffuse angular radial and coordination chemistry of the transition metals. A prime
function. Relativistic effects also contribute to the lanthanide example of the difference in actinide chemistry is the
and actinide contractions. With heavy atoms, the core electrons pervasiveness of the linear dioxo unit, which is unmatched in
approach speeds that are close to the speed of light. When transition metal chemistry. For the actinides, the trans dioxo
these fast rates are obtained, the mass of the electron increases structure is maintained through different metal ions, oxidation
as described by the special theory of relativity. The mass of states, and valence electron counts, for example, UO2 2+/+
(f 0 /f1 ), NpO2 2+/+ (f1 /f 2 ), PuO2 2+/+ (f 2 /f 3 ) and AmO2 2+/+
1.10
(f 3 /f 4 ). In transition metal dioxo complexes, MO2 Lx , the oxo
ligand geometry (cis or trans) is almost entirely dependent
1.05 An3+ on the electron count. For ReO2 (CH3 )3 (d0 system) (17), the
oxo ligands are cis in order to maximize the -bonding,
1.00
while the oxo ligands in ReO2 (py)4 (d2 system) (18) are found
An4+
Ionic radii ()
t1u 7p
eg
a1g 7s
0 d
6p t1u
eg
t2g 6d
6s a1g
0 d t2g + eg
5d t2g 5f
t2g + eg a2u + t1u + t2u
Lp
a1g + eg + t1u
ML
a1g + eg + t1u a1g + eg + t1u
u Pu4+ + PuO2 +
Pu3+ + PuO2 2+ (1)
UO Pu4+ + 2H2 O
Pu3+ + PuO2 + + 4H+ (2)
g O 2p
g
The reduction potentials are also dependent on the pH of
UO the solution. Dramatic changes in the redox potentials of Np
u
and Pu have been observed on progressing from acid (1 M)
u to base (1 10 M). For example, the reduction potential for
6p NpVII /NpO2 2+ is reduced by nearly 2 V! Scheme 3 shows the
u reduction potentials for Np and Pu at either 1 or 10 M NaOH
solutions. As can be seen, the potentials are such that the
Redox couple Ac Th Pa U Np Pu Am Cm
An2+ /An0 0.7 +0.7 +0.3 0.1 0.3 1.2 1.95 1.2
An3+ /An2+ 4.9 4.9 5.0 4.7 4.7 3.5 2.3 3.7
An3+ /An0 2.13 1.66 1.79 2.00 2.07 2.06
An4+ /An0 1.83 1.47 1.38 1.30 1.25 0.90
An4+ /An3+ 3.8 1.4 0.52 +0.15 +1.01 +2.62 +3.1
AnO2 /An0 2.56
AnO2 + /An4+ 0.05 +0.38 +0.67 +1.04 +0.82
AnO2 + /An3+ +1.72
AnO2 2+ /AnO2 + +0.17 +1.24 +0.94 +1.60
AnO2 2+ /An4+ +0.27 +0.94 +0.99 +1.21
Redox couple Bk Cf Es Fm Md No Lr
AnVII /AnO2 2+ +2.04
An2+ /An0 1.54 1.976 2.2 2.5 2.5 2.6
An3+ /An2+ 2.8 1.6 1.55 1.15 0.15 +1.45
An3+ /An0 1.96 1.91 1.98 2.07 1.74 1.26 2.1
An4+ /An3+ +1.67 +3.2 +4.5 +5.2
12 ACTINIDES: INORGANIC & COORDINATION CHEMISTRY
higher oxidation states can be stabilized in aqueous solutions, The emission spectroscopy is also used to study the
including the heptavalent ions of Np, Pu, and possibly Am. speciation of the actinides. Compounds with isotopes of
It should be noted that this phenomenon follows the expected uranium, americium, and curium fluoresce in the visible range,
trend based on an increase in the electron density on the metal making detection relatively easy. Neptunium and plutonium
center with changing the speciation from AnO2 (H2 O)x 2+ in fluoresce in the near-infrared region, and recent developments
acidic conditions to AnO2 (OH)4/5 2/3 in highly alkaline in detectors may allow for more facile measurements. The
solutions. power of emission spectroscopy is the ability to run at variable
The equilibria and variety of species discussed above would temperatures and low concentrations in both solution and
seem to make studying the specific oxidation states of actinides solid phases. The luminescence from the actinide complexes
difficult. However, through careful control of the conditions, is strongly dependent on both energy and lifetime of the
oxidation state pure solutions for all of the actinides can be speciation products. In a similar fashion as the absorption
obtained for synthetic, quantitative and/or qualitative studies. spectra of UO2 2+ , vibronic coupling occurs. The primary
difference between the two is that in the emission spectra the
ground-state vibrations of the AnO2 2+ are probed.
The ubiquitous linear dioxo unit gives an excellent handle to
6 CHARACTERIZATION OF ACTINIDE use vibrational spectroscopy in studying the speciation of high-
COMPLEXES valent aqueous complexes of the actinides. Both IR and Raman
spectroscopy have been utilized. For IR, the observation of
the stretching frequencies of the dioxo unit are complicated by
The radioactive nature of the actinides, especially the the relatively small window available for water. Attenuated
transuranics, can introduce significant challenges in the total reflectance cells have significantly aided the examination
characterization of their complexes. In order to prevent of aqueous actinyl complexes by providing the requisite
contamination, multiple layers of containment are often background subtraction. Raman spectroscopy does not have
required, which can limit the types of studies that can be the same issues when measuring actinide complexes in water.
undertaken. However, a suite of spectroscopic tools has For actinyl complexes, the 1 stretch is dependent on ligands in
been used to study the chemistry and speciation of the the equatorial plane. In general, the 1 stretch of the O=An=O
actinides. A partial list of these techniques includes absorption, weakens with the addition of better - or -donor ligands.
emission and vibrational spectroscopies, X-ray absorption and Nuclear magnetic resonance (NMR) techniques have been
diffraction, and multinuclear magnetic resonance. increasingly used for studying the actinides. Th(IV), U(VI),
The absorption spectroscopy in the UV-Vis-NIR is and Np(VII) complexes are diamagnetic, and a range of
especially rich for the actinides, allowing for fairly simple multinuclear methods can be used, including 13 C, 1 H, 19 F,
determinations of the metal oxidation state. The primary and so on. Most complexes with the other actinides and other
absorption bands result from f f transitions, f d and oxidation states of uranium and neptunium are paramagnetic.
ligand-to-metal charge transfers. The f f transitions are The paramagnetism causes a shift and broadening of the NMR
typically weak since they are forbidden under the LaPorte signals similar to transition metal species. One of the nuclei
selection rules. Distortions in symmetry allow for relaxation that has relatively narrow lines for paramagnetic complexes is
in these rules and bands in the visible to near-infrared the quadropolar 17 O. The oxo groups of the actinyl ions can
range result. Complexes that contain an inversion symmetry, be labeled with 17 O by reducing the metals to the tetravalent
for example PuO2 Cl4 2 , have weaker f f transitions state and reoxidizing to the penta- or hexavalent state in an
( < 20 M1 cm1 ). The direct interactions of the 5f orbitals 17
O-enriched aqueous solution. Unlike the transition metals,
with the ligand set generally make the absorption bands the actinide complexes that have the narrowest line-widths are
broader than the absorption spectra of comparable lanthanide those with either an f 0 or odd f-electron configuration. For
species. The charge transfer bands in actinide complexes can example, NpVII (f 0 ) and NpO2 2+ (f1 ) have visible 17 O-NMR
be intense and lead to the variety of colors observed for the peaks, whereas the peaks for NpO2 + (f 2 ) are so broad that
actinides with varying oxidation states or ligands. Vibronic they cannot be observed.
coupling also plays a significant role in the absorption spectra Another technique that has been increasingly used for
of actinide complexes. The prime example of this vibronic determining actinide speciation is X-ray absorption. These
coupling is observed in the visible spectra of UO2 2+ species. measurements are typically made at synchrotron radiation
In these complexes, the 1 stretching mode (800 900 cm1 ) laboratories where extremely high energy X-rays (15 25 keV)
resulting from an excited state of the linear dioxo unit couples with high fluxes can be generated and used to interrogate a
with the absorption manifold to give the appearance of multiple sample. The techniques are element specific, which allows
peaks with approximately the same energetic separation. for the ability to probe heterogeneous samples, for example
Absorption techniques have been used extensively in studying environmental substances. The X-ray absorption near edge
the aqueous chemistry of the actinides, especially when linked spectrum (XANES) is able to give information on the oxidation
with potentiometric titrations. state of the actinide. For example, a linear relationship between
ACTINIDES: INORGANIC & COORDINATION CHEMISTRY 13
the edge energy and oxidation state of plutonium has been pentavalent ions in line with an increase in the ionic radii with
reported. The structure near the absorption edge can also shed the change in oxidation state.
light on the structure of the actinide, for example, presence of Tetravalent ions of the actinides can be stabilized in
an actinyl unit. The variability in the ligands can also cause aqueous solutions for Th to Am. Owing to the more intense
a shift in the edge position; however, this is typically a much radiation fields generated by Am, maintaining oxidation state
smaller effect than the oxidation state. The X-ray absorption pure samples is difficult ( radiolysis spontaneously promotes
fine structure (XAFS) that results after the primary absorption the reduction of AmIV to AmIII ). For those ions that have
can be used to give structural information. This technique been studied, complexes of the form An(H2 O)x 4+ (An = Th,
essentially gives the ability to obtain data from any solid or U, Np, Pu; x = 9 12) have been proposed. The most widely
solution similar to that gained from a single-crystal X-ray accepted values for the number of H2 O molecules bound to
diffraction study. The primary difference is that no angular the metal center are 10 for Th and 9 for U to Pu. The An OH2
information can be determined from XAFS, but the type, distances in these ions range from 2.50 to 2.46 A.
number, and bond distances of atoms bound to a metal can be. The trivalent plutonium aquo ion, [Pu(H2 O)9 ]3+ , has been
crystallized with nine H2 O ligands in a tricapped trigonal
prismatic geometry.4
Salts of oxo anions, such as nitrate, sulfate, perchlorate,
iodate, hydroxide, carbonate, phosphate, oxalate, and so
7 AQUEOUS COORDINATION COMPLEXES
on, are important for the separation and reprocessing
of technologically important actinides, while hydroxide,
The most basic coordination complex in aqueous solutions carbonate, and phosphate ions are important for the chemical
is the aquo ion. For most metals in the periodic table that behavior of the actinides in the environment. The general
form ions in aqueous solutions, the coordination number and trends of complexes formed in aqueous solutions are as
geometry of the aquo ion is well known. For a majority follows:
of the actinides, controversies still exist as to the exact
number of H2 O molecules that are bound to the metal for AnO2 n+ (n = 1, 2) complexes: as H2 O is replaced as
centers. The uncertainty in the structures is linked to the a ligand by better -, -, or ionic donors, for example,
limited number of crystal structures that exist for actinide OH , F , Cl , CO3 2 , the An=O distance increases and
aquo complexes. This lack of data is related to the difficulty the 1 decreases;
in crystallizing materials from aqueous solutions. The most on transitioning between AnO2 + to An4+ : the lack of the
well studied aquo ion of the actinides is UO2 (H2 O)5 2+ . This linear dioxo unit in the lower valent complexes results in
ion has been crystallized from noncoordinating perchloric a slight decrease in the An L bond distance;
acid solutions through either concentration or addition of the determination of end members for a specific ligand in
18-crown-6. For the latter case, the crown ether interacts an aqueous-based actinide system will be the easiest to
with the H2 O molecules bound to the uranium through determine because of the ubiquitous presence of multiple
hydrogen bonds. These same crystallization techniques have equilibria, for example, UO2 Cl2 (H2 O)2 , UO2 Cl3 (H2 O) ,
been attempted to obtain crystal structures of the hexavalent and UO2 Cl4 2 for the uranyl chloride system.
Np, Pu, and Am ions; however, X-ray quality single crystals
of the aquo ions have not been obtained, sometimes due to 7.1 Nitrates
oxidation state changes or inner-sphere complexation by the
crown ether. From EXAFS, structural data on the aquo ions Hexavalent. Nitrate complexation with actinide ions
have been obtained for the hexavalent ions, AnO2 (H2 O)5 2+ is very weak, and the determination of the formation
(An = U Am). For calibration purposes, the bond distance constants for aqueous nitrate solution species is extremely
for the oxo ligands of the UO2 2+ species obtained from XAFS difficult. Under aqueous conditions with high nitric acid
and single-crystal analyses show a nearly identical length. concentrations, complexes of the form AnO2 (NO3 )(H2 O)x + ,
The bond An = O distance was found to be 1.76, 1.75, 1.74, AnO2 (NO3 )2 (H2 O)2 , and AnO2 (NO3 )3 (An = U, Np, Pu)
and 1.80 A for An = U, Np, Pu, and Am, respectively. The are likely to be present. Solids of the anionic trisnitrato
An OH2 distance for the same complexes was found to be complex have been isolated for U and Np5,6 however,
2.42, 2.42, 2.41, and 2.40, respectively. minimal structural data have been obtained. Solid uranyl
For those actinides stable in the pentavalent state, ions of nitrate, UO2 (NO3 )2 xH2 O, is obtained as the orthorhombic
the form AnO2 (H2 O)x + (An = Np, Pu; x = 4, 5, 6) have been hexahydrate from dilute nitric acid solutions and as the
postulated. PaV is not included in this list since it readily trihydrate from concentrated acid. The Np analog can
hydrolyzes in aqueous solutions to form Pa2 O5 xH2 O. All of be precipitated from a mixed aqueous HNO3 and MeCN
the structural data for these complexes come from XAFS. The solution by the addition of 18-crown-6. Multiple structural
bond distances for both An=O (1.83 A for both Np and Pu) determinations have been made for the hexavalent uranium
and An OH2 (2.51 and 2.5 A, respectively) expand in the nitrate complexes, and all show the common formula unit of
14 ACTINIDES: INORGANIC & COORDINATION CHEMISTRY
UO2 (NO3 )2 (OH2 )2 (19) with a local hexagonal bipyramidal compounds AnO2 (SO4 )2.5H2 O (An = Np, Pu) have been
coordination about the central uranyl ion. The average An=O isolated and characterized by the X-ray analysis, which
bond distances for the actinyl dinitrate complex were found confirmed comparable structures with the U analog. A
to be 1.76 and 1.74 A for U and Np, respectively, while the number of ternary An(VI) sulfates of the general formula
An OH2 distances (2.44 A) and An Onitrate (2.49 A) distances (M)k (AnO2 )m (SO4 )n xH2 O, where M = monovalent cation,
were identical for the two actinides. The actinyl dinitrato that is, NH4 or alkali metals, M(AnO2 )m (SO4 )n xH2 O, where
complex is also known to bind other neutral donors to form M = bivalent cation, such as alkaline-earth or transition
compounds of the form AnO2 (NO3 )2 L2 (L = TBP, MeCN, metals (Mn, Cd, Hg), have been reported. In one of the
DMF, MeCO2 Et, etc.). As with all of the other neutral adducts, more simplistic systems, K4 UO2 (SO4 )3 , each uranium has
the technologically important AnO2 (NO3 )2 (TBP)2 (An = U, a pentagonal bipyramidal geometry with five-coordinated
Np, Pu) (20) complex displays trans nitrate ligands with the oxygen atoms from four sulfate groups in the equatorial
TBP ligands occupying the same coordination sides as H2 O plane. The crystal structure for Cs2 NpO2 (SO4 )2 is composed
in (19). of anionic layers of [NpO2 (SO4 )2 ]n 2n with bridging sulfate
groups.
In addition to traditional aqueous chemistry to produce
BunO
actinide sulfate phases, hydrothermal synthetic methods have
O O BunO P O been utilized. The novel phases, [N2 C5 H14 ]2 [UO2 (SO4 )3 ],
H2O O N O O N O
O U O BunO O U O [N2 C5 H14 ][UO2 (H2 O)(SO4 )2 ], [N2 C4 H14 ][UO2 (SO4 )2 ], and
OH2 O OBun [N2 C4 H14 ][(UO2 )2 (H2 O)(SO4 )3 ]H2 O have been synthesized
N O N O P
O O O O OBun by high-temperature organic-templated reactions.
OBun
(19) (20)
Pentavalent. Protactinium is known to bind sulfate in
solutions of H2 SO4 ; however, very limited data are available
Pentavalent. The complexation of the Pa and Np
on the molecular species. Sulfate complexes with the general
pentavalent ions by nitrate is known; however, limited
formula of NpO2 (SO4 )n 12n (n = 1 3) have been reported. In
thermodynamic and structural data are known. For Pa,
most of these complexes, the Np is found in a seven-coordinate
mixed hydroxo/nitrato or oxo/nitrato complexes have been
pentagonal bipyramid geometry.
proposed. The presumed structure for the NpV species is
NpO2 (NO3 )(H2 O)x .
Tetravalent. The AnIV (An = Th, U, Np and Pu) sulfate
Tetravalent. Nitrate complexes for tetravalent actinides, system has also been studied in strongly acidic solutions.
for example, Th and Pu, are extremely important in An(SO4 )2 xH2 O (x = 4, 6, 8, 9) can be precipitated from weak
actinide separation and purification processes. The limiting and concentrated sulfuric acid solutions. For An(SO4 )2 4H2 O
species in the nitrate series is the hexanitrato complex, (An = Th, U, Np, Pu), the actinide atoms are surrounded
An(NO3 )6 2 .7 There is reasonable evidence for the formation by a square antiprism of O atoms, with each An bonded to
of aqueous U(IV) nitrate complexes of the general formula four molecules of water and linked by bidentate bridging
U(NO3 )n 4n , where n = 1 to 4. However, owing to the sulfate groups to other metal atoms. In these compounds,
inherent weakness of the complexes, quantitative data on the bond distances observed for the An Ophosphate are
the formation constants is only available for U(NO3 )3+ and significantly shorter than the An OH2 , for example, 2.308 A
U(NO3 )2 2+ . No neutral U(IV) nitrates have been obtained and 2.361 A, respectively for the Np compound. Ternary
from aqueous solutions, but a number of anionic complexes of An(IV) sulfates have also been described in the literature.
general formula M2 [U(NO3 )6 ], where M = NH4 , Rb, Cs, and Many of the compounds have layered structures and/or unusual
M[U(NO3 )6 ]8H2 O, where M = Mg, Zn, have been isolated coordination environments. The trisulfate of Np(IV) has been
and characterized. These solids contain the 12-coordinate isolated as a Cs salt, Cs2 Np(SO4 )3 2H2 O. In this compound,
anionic U(IV) center. Neutral, U(IV) nitrate complexes of the NpIV cation is coordinated to nine oxygen atoms in an
formula U(NO3 )4 L2 (L = OP(C6 H5 )3 , OP(NC4 H8 )3 ) have irregular geometry. The structure of K4 Pu(SO4 )4 2H2 O was
also been isolated from aqueous solutions and structurally determined from powder diffraction and consists of dimeric
characterized. units of [(2 -SO4 )3 Pu(2 -2 -SO4 )2 Pu(2 -SO4 )3 ]8 .8
7.2 Sulfates Trivalent. The trivalent ions of the actinides have been
found to bind sulfate ions. The simple hydrated sulfate salt,
Hexavalent. The aqueous actinyl sulfate systems have An2 (SO4 )3 xH2 O has been proposed for U, Np, Pu, Am,
been widely studied for uranium and complexes of formula and Cm. A crystal structure of Am2 (SO4 )3 8H2 O showed
AnO2 (SO4 )n 22n , where n = 0, 1, and 2, are likely to significant cross-linking of the Am atoms through sulfate
be formed in solution. For the transuranics, the neutral ligands and an extensive hydrogen bonding network. The
ACTINIDES: INORGANIC & COORDINATION CHEMISTRY 15
coordinate sphere of the Am atoms is composed of eight Hexavalent. As with most reactions, the hydrolysis of
oxygen atoms, four from sulfate ions and four from H2 O UO2 2+ is the best studied of the hexavalent actinides. The
molecules. The Am Osulfate distances ranged from 2.38 to hydrolysis of UO2 2+ begins at pH 3, while the onset
2.95 A while the Am OH2 distances varied from 2.41 to for the hydrolysis of NpO2 2+ and PuO2 2+ each occur at
2.55 A. Ternary complexes of the trivalent actinides are also a higher pH. The monomeric hydrolysis products of the
known. For example, MPu(SO4 )2 xH2 O has been isolated uranyl ion, UO2 (OH)n 2n (n = 1, 2) can be studied in
with a number of alkali metals and ammonium. The Pu in solutions with uranium concentrations less than 104 M. For
these compounds is nine-coordinate and is analogous to the solutions with higher uranium concentrations, multinuclear
lanthanide compounds of the same formula. It is interesting cationic species dominate the speciation, for example,
to note that the UIII sulfates, U2 (SO4 )3 xH2 O (x = 2, 5, 8) (UO2 )2 (OH)2 2+ , (UO2 )3 (OH)4 2+ , and (UO2 )3 (OH)5 + . These
and M2 U2 (SO4 )4 are essentially the only available salts of cations have been crystallized from solutions with the
trivalent uranium. formulas (UO2 )2 (2 -OH)2 (OH2 )6 2+ and (UO2 )3 (3 -O)(2 -
OH)3 (OH2 )6 + (21). For Np and Pu, the dimer of the first
hydrolysis product, (AnO2 )2 (OH)2 2+ (22), has also been
7.3 Hydroxides identified but not fully structurally characterized.
distances for U, Np, and Pu are 1.82, 1.80, 1.77 A, respectively, have been reported are AnO2 (CO3 ) , AnO2 (CO3 )2 3 , and
while the average An OH distances are 2.26, 2.24, and 2.29 A AnO2 (CO3 )3 5 . As with all of the actinyl complexes, the
respectively. carbonate ligands bind in the equatorial plane and in a
bidentate fashion. As a result, the likely coordination geometry
Heptavalent. In highly alkaline solutions ([OH ] = for the mono- and biscarbonato complexes in solution is a
0.5 18 M), the redox potentials for Np and Pu have shifted pentagonal bipyramid, while the triscarbonato complex has
to the point that the heptavalent state can be stabilized for a a hexagonal bipyramidal geometry. When crystallized, the
limited time in aqueous solutions. The lifetime of the AnVII mono- and biscarbonato complexes condense, allowing the
species is dependent on the base concentration; however, carbonate ligands to bridge multiple actinide centers and
in general, NpVII is significantly more stable than PuVII , typically resulting in a hexagonal bipyramidal geometry.
for example, weeks versus days, respectively. Over the past
few years, a significant interest has evolved in studying the Hexavalent. The aqueous An(VI) carbonate system has
structure of the heptavalent actinide ions. Two forms of NpVII been well studied. A multitude of An(VI) carbonate complexes
have been crystallographically characterized, NpO4 (OH)2 3 have been identified, including monomeric, multinuclear, and
and NpO4 . The latter anion was isolated as a salt with Na+ mixed hydroxo carbonato complexes. The monomeric mate-
and K+ cations. The structure of KNpO4 is layered with the Np rials generally have the form AnO2 (CO3 )n 22n (n = 1 3).
atoms bound to two oxo-type ligands (Np=O 1.?? A) in axial The end member of the carbonate series, AnO2 (CO3 )3 4 (23),
positions and four bridging oxygen atoms (Np O 2.?? A) that has a hexagonal bipyramid geometry with the three biden-
make up the plane of the layer. The former complex has four tate carbonates occupying the equatorial plane. The mono-
shorter bonds (1.88 A) corresponding to the four Np=O and and biscarbonato complexes are typically five coordinate,
two longer bonds Np OH (2.33 A) (14). This planar teraoxo with bidentate carbonate ligands and either three or one
arrangement is unique to heptavalent actinides having no H2 O molecule. Under conditions with high actinide metal
transition metal or f element analogs. concentrations, multinuclear species can predominate, for
example (AnO2 )3 (CO3 )6 6 (24). The U(VI) is the best stud-
ied of the hexavalent actinide carbonate complexes. The
7.4 Carbonates known uranium(VI) carbonate solids have empirical formulas
UO2 (CO3 ), M2 UO2 (CO3 )2 , and M4 UO2 (CO3 )3 (M = Na+ ,
Actinide carbonate complexes are of interest not only
K+ , Rb+ , Cs+ , NH4 + , etc.). The monocarbonato compound,
because of their fundamental chemistry and environmental
UO2 (CO3 ), is a mineral known as rutherfordine, and its struc-
behavior but also because of extensive industrial applications,
ture has been determined from crystals of both the natural
primarily in uranium recovery from ores and nuclear fuel
mineral and synthetic samples. Rutherfordine is a layered
reprocessing.
solid in which the local coordination environment of the
uranyl ion consists of a hexagonal bipyramidal arrangement
Trivalent. The trivalent actinides form simple carbonates
of oxygen atoms. Each uranium atom forms six equatorial
of the formula An2 (CO3 )3 . When these solids are dissolved
bonds with the oxygen atoms of four carbonate ligands, two
in aqueous solutions of alkali metal carbonates, anionic
in a bidentate manner and two in a monodentate manner. The
complexes are formed, for example An(CO3 )n 32n (n = 2 4).
biscarbonato complex has been shown to form a trimeric anion
Tetravalent. The best-studied tetravalent actinide carbon- of the form (UO2 )3 (CO3 )6 6 (7). This molecule possesses a
ato complex is An(CO3 )5 6 (An = Th, U, Pu). This anion has D3h planar structure in which all six carbonate ligands and
been isolated using a variety of cations, including Na+ , K+ , the three uranium atoms lie within the molecular plane. The
Tl+ , [Co(NH3 )6 ]3+ and C(NH2 )3 + /NH4 + . In solution, the six uranyl oxygen atoms are perpendicular to the plane, with
pentacarbonato complex is the end member of the series three above, and three below the plane. The local coordination
An(CO3 )n 42n (n = 1 5); however, in the mineral tuliokite, geometry about each uranium is hexagonal bipyramidal.
Na6 BaTh(CO3 )6 6H2 O, thorium exists as a hexacarbonato
complex. The analysis of the thermodynamic data for these 6
O O
actinide carbonate systems has led to differences of opinion O O O O O O
on the actual speciation. The data appear to support both O U O U O
O O 4
the stepwise addition of CO3 2 and subsequent loss of H2 O
molecules within the An4+ cation coordination sphere as well O O O O O O O O O
O An O
as the formation of mixed hydroxo carbonato complexes, for O O O O O U O
example Pu(CO3 )3 (OH)3 . O
O O O
Pentavalent. The binding of carbonate to pentavalent
actinide ions has been studied for most of the light O
actinides (An = U, Np, Pu, Am). The primary species that (23) (24)
ACTINIDES: INORGANIC & COORDINATION CHEMISTRY 17
7.5 Phosphates For the larger chloride ion, the final member in the series
is the tetrachloride, AnO2 Cl4 2 . The uranium, neptunium,
Inorganic phosphate ligands are important with respect and plutonium tetrachloride dianions have been isolated with
to the behavior of actinides in the environment and as a number of different cations, for example, Na+ , NH4 + ,
potential waste forms. There have been a number of K+ , Cs+ , K+ 18-crown-6, and so on. The An=O distances
experimental studies to determine the equilibrium constants were found to be 1.768, 1.751, and 1.737 A for An = U,
in the actinide phosphoric acid system, but they have been Np, and Pu, respectively. The An Cl distances in these
complicated by the formation of relatively insoluble solid complexes is virtually unchanged: 2.675 A (U), 2.659 A
phases and the formation of ternary actinide complexes in (Np), and 2.656 A (Pu). These structural data suggest that
solution. the chloride ligands are bound in essentially a purely ionic
The chemistry of the phosphate system is complicated by manner while the covalent nature of the An=O bond is
the number of different ligands that are possible. In acidic preserved.
solution (hydrogen-ion concentration range 0.25 2.00 M), The lower valent actinide ions also bind the halides
H3 PO4 and H2 PO4 are potential ligands, whereas in to form cationic complexes, for example, AnXn (H2 O)m zn
neutral to basic solution, HPO4 2 and PO4 3 ligands are (z = 3, n = 1 6; z = 4, n = 1 7)9 and AnO2 Xn (H2 O)m 1n
predominant. The phosphate salts are slightly soluble in water (n = 1 4).
and dilute mineral acids. The synthetic methods to obtain
solid phases of actinide phosphates include precipitation and
high-temperature methods. 7.7 Multidentate Ligands
The trivalent actinides form simple insoluble phos-
phate salts of the form, AnPO4 xH2 O. Tetravalent actinides Polycarboxylic Acids. Carboxylic acids have been found
form a number of different phases including metaphos- to bind strongly to actinide ions. The primary binding mode
phates An(PO3 )4 , the pyrophosphate An(P2 O7 ), double for the carboxylic acids is bidentate. The affinity of the
phosphates MAn2 (PO4 )3 and M2 An(PO4 )2 , and orthophos- low-valent actinides with these ligands increases with the
phates, An(HPO4 )2 xH2 O. Phosphates of the hexavalent density of the ligand, for example, ethylenediaminetetraacetate
actinyl ions also form complex complexes and solid phases. (EDTA) > acetate. For An4+ , the EDTA ligand is hexadentate
The predominate compounds include AnO2 (HPO4 )xH2 O, with a twist conformation. Diethylenetriaminepentaacetate
orthophosphates M(AnO2 )n (PO4 )m xH2 O, hydrogenphos- (DTPA) has an even higher affinity for both An3+ and An4+
phates M(AnO2 )n (Hk PO4 )m xH2 O, pyrophosphates Anm On - ions.
P2 O7 , metaphosphates (AnO2 )n (PO3 )m xH2 O, and poly-
phosphates (AnO2 )n (Pa Ob )m xH2 O. Crown Ethers. The crown ether macrocycle, for example,
18-crown-6, has been found to coordinate An3+ and An4+ in
both aqueous and nonaqueous conditions via an inner-sphere
7.6 Halides
mechanism. For UO2 2+ , multiple compounds that contain
The best-studied aqueous actinide halide systems are the crown ether ligands have been isolated. In most of these
fluorides and the chlorides. Fluoride and chloride ions are compounds, the crown ether interacts in an outer-sphere
added to the actinyl centers in a stepwise fashion (Scheme 4). manner, engaging in hydrogen bonding with the ligands on
The end member in the actinyl fluoride system is the the metal center. Inner-sphere coordination of UO2 2+ occurs
pentafluoride, AnO2 F5 3 . For the uranyl analog, the U = O only under strictly anhydrous conditions. For the Np system,
and U F bond distances were found to be 1.79 and 2.18 A the presence of a crown ether in aqueous solutions causes
respectively. The uranium tetrafluoride ion, UO2 F4 2 , has a reduction of the metal center from NpVI and NpV and
been isolated as a dimer with two bridging fluoride ligands. a spontaneous inner-sphere coordination of the crown ether
The U = O, U Fterminal , and U Fbridging distances for this to form NpO2 (18-crown-6)+ . The linear dioxo unit in this
complex were found to be 1.79, 2.15 to 2.20 A, and 2.30 A, complex sits perpendicular to the plane created by the six
respectively. oxygen atoms of the crown ether molecule. The average
Np=O distance for this complex is 1.85 A and the average
Np Ocrown distance is 2.?? A.
F F
AnO2(H2O)52+ AnO2F(H2O)4+ AnO2F2(H2O)3
F
8 NONAQUEOUS COORDINATION COMPLEXES
AnO2F53 AnO2F4(H2O)x2 AnO2F3(H2O)x
F F
The coordination chemistry of the actinides, especially
thorium and uranium, continues to be of great interest.
Scheme 4 Considered hard metal ions, An(III to VI) have the
18 ACTINIDES: INORGANIC & COORDINATION CHEMISTRY
greatest affinity for hard donor atoms such as N, O, thiocyanates, and polypyrazolylborates. A majority of the pub-
and the light halides. Tetravalent thorium and tetra- and lished work with these ligand sets has been with complexes of
hexavalent uranium, neptunium, and plutonium coordination Th and U; however, some complexes of Np and Pu have also
complexes are the most common; however, trivalent and been reported.
pentavalent complexes are being identified with increasing
frequency. As with all of the actinides, the ionic radii of Trivalent. The study of trivalent light actinide coor-
the ions are significantly larger compared to a transition dination complexes with N-donors is complicated by the
metal ion in an identical oxidation state. The result of relative ease of oxidation. Some examples of the iso-
this increased ionic radius is an expansion of the possible lated materials include AnX3 (NH3 )n (X = Cl, Br), AnI3 py4 ,
coordination environments (3- to 14-coordinate) and electron AnI3 (tmed)2 , and AnCl3 (CH3 CN). The homoleptic complexes
counts (up to 24 electrons). The structure and bonding [An(CH3 CN)9 ]3+ (An = U, Pu)11 have been synthesized by
in the nonaqueous complexes of the actinides like that dissolution of UI3 (THF)4 and oxidation of plutonium metal
of the aqueous complexes involves a mixture of ionic in CH3 CN. Both complexes have a nine-coordinate trigonal
and covalent bonding. While it is impossible to positively prismatic geometry. The pyramidal tris-silylamido complexes,
correlate which orbitals are being utilized or if bonding An[N(Si(CH3 )3 )2 ]3 (An = U, Np, Pu)10,12 (25) have been syn-
is covalent or ionic, the fact that the 5f elements form thesized and have been shown to be useful starting materials
complexes with ligands like N2 and CO suggests that a for the synthesis of other trivalent or tetravalent compounds.
significant covalent component is present in the complex Other less bulky trisamido AnIII complexes, for example,
formation. U[N(R)Ar]3 (R = Bu and Ar = 3-5-Me2 C6 H3 ), have been
shown to elicit some interesting chemistry. When the
U(NRAr)3 complex is produced in situ by reduction of
8.1 Starting Materials
UI(NRAr)3 in the presence of Mo[NPh(t-Bu)]3 and N2 ,
Choosing, obtaining, or synthesizing the appropriate an end-on N2 -bridged complex of the form [(NRAr)3 U(-
starting material is critical in order to investigate the N2 )Mo13 3 ].
13
A similar reaction has also been found with
coordination chemistry of the actinides in nonaqueous cyanoimide where a dinuclear uranium complex was isolated,
environments. For thorium, the two most common starting (2 ;1 ,1 -NCN){U[N(R)Ar]3 }2 (26).14
materials are ThCl4 and ThBr4 (THF)4 . In synthesizing
ThBr4 (THF)4 , thorium metal is reacted with two equivalents Ar Bu BuAr
of Br2 in THF at 0 C. This reaction can be run on very Bu
large scales, 100 to 200 g product. For uranium, neptunium, N N
N
An Ar
and plutonium, the three common starting materials for tri-, (Me3Si)2N N(SiMe3)2 U NCN U
tetra- and hexavalent complexes are AnI3 (THF)4 , AnCl4 , and N(SiMe3)2 Bu N N
AnO2 Cl2 (An = U, Np, Pu), respectively. The first material, N Bu
Bu
AnI3 (THF)4 , is prepared in THF at 0 C by adding I2 to Ar Ar Ar
metal chips or turnings.10 The uranium analog is deep purple, (25) (26)
the neptunium is orange, and the plutonium analog is off-
white. The synthetic routes to obtain AnCl4 are provided
in Section 9. For the green UCl4 , the preferred synthetic Another ligand that has received considerable attention
method involves the reaction of UO3 with hexachloropropene. in actinide chemistry over the past few years is tren-
For the hexavalent starting material, AnO2 Cl2 , the most or trisamidoamine, [N(CH2 CH2 N)SiMe2 But ]3 (NN3 ).1520
efficient synthetic route is the oxidation of AnCl4 with O2 This ligand forms more stable complexes than the trisamido
at 350 C. complexes owing to the forced facial coordination and the
chelate effect. The purple U(NN3 ) can be synthesized by
reduction of the tetravalent UI(NN3 ) complex with K in
8.2 Nitrogen Donors pentane or by fractional sublimation of [{U(NN3 )}2 (-Cl)].
Lewis bases adducts, for example, pyridine, HMPA, of
The coordination chemistry of the light actinides U(NN3 ) have been isolated. The oxidation of U(NN3 ) or
with N-donating ligands is one of the better-studied its derivatives using trimethylamine N-oxide gives rise to UIV
areas. Numerous N-donor ligands have been com- and UV complexes of the form, [18 2 (-O)] and U(NN3 )O,
plexed with the actinides, including neutral mono-, respectively. As with the other trisamido complexes, U(NN3 )
bi-, and polydentate ligands, that is, ammonia, pri- reacts reversibly with N2 to give a side-on bound product,
mary, secondary, and tertiary amines, alkyl aryldiamines [16 2 2 2
2 ( - : -N2 )]. While the N N bond distance in this
(en = ethylenediamine, 1,4-diaminobenzene), N-heterocycles complex is essentially the same as in free dinitrogen, the
(py = pyridine, bipy = bipyridine, terp = terpyridyl), nitriles preference for the side-on over end-on bonding is explained
(CH3 CN), anionic amides ([N(C2 H5 )2 ] , [N(Si(CH3 )3 )2 ] ), on the basis of covalent interactions where the dinitrogen p
ACTINIDES: INORGANIC & COORDINATION CHEMISTRY 19
orbital is a better -donor than the p orbital to trivalent (An = Th, U, Np)32 to form molecular compounds. In these
uranium.21 complexes, the Fe(CN)6 octahedra are maintained with the An
Polypyrazol-1-yl borates of the form U(HBpz3 )m I3 m ion binding the N atoms of the ferrocyano ligands.
(THF)n (m = 1, n = 2; m = 2, n = 0) and [PuCl(-Cl)22 -
(Me2 pzH)]2 22 have been reported. For the (UI[HB(Me2 pz)3 ])2 Pentavalent. A limited number of pentavalent actinide
complex, the pyrazolyl borate ligand binds in an unusual complexes have been isolated with N-donor ligands. The
side-on fashion. primary reason for this is the inability of Th to attain the
pentavalent state and the propensity of UV complexes to
Tetravalent. A number of coordination complexes of disproportionate into UIV and UVI complexes. Some of the
AnIV with N-donor ligands have been characterized. typical complexes that have been reported are adducts of
Traditional adducts of AnX4 (An = Th, U, X = halogen, U(OR)5 and UX5 with the ligands described for the tri- and
alkoxide) have been isolated with a variety of neutral N- tetravalent actinide complexes.
donor ligands, for example, monodentate (ammonia, primary Homoleptic amido compounds of UV , U(NR2 )5 , have been
to tertiary amines, nitriles, isocyanides, N-heterocyclics) and synthesized by oxidation of anionic tetravalent complexes,
bidentate (diaminoalkanes, diaminoarenes, N-heterocyclics). [U(NR2 )5 ] . A unique hexakisamido UV complex has been
The coordination numbers for these complexes generally range isolated using 2,3:5,6-dibenzo-7-azabicyclo[2.2.1]hepta-2,5-
from 8 to 12. As with transition metals, increasing the steric diene. The [U(dbabh)] anion can be oxidized to form a UVI
bulk of the ligands can lead to lower coordination numbers, species both of which have a near-perfect octahedral geometry
for example, An(OR)4 (NH3 )n (R = alkyl, aryl; n = 1, 2). with the six amido ligands.33
Amido complexes of AnIV are highly reactive to insertion The oxidation of tetravalent or reduction of hexavalent
reactions and protonation. For example, [An(NR2 )4 ]n (R = uranium compounds with the tren ligand present can
alkyl, aryl)23 undergo insertion reactions with CO2 , COS, produce stable UV complexes. The one-electron oxidation
CS2 , and CSe2 to form carbamate complexes and react of [U(NN3 )(OBut )(OPh)Li-(THF)] by either electrolysis or
with alcohols to form alkoxide complexes. The structure chemical means yields the neutral [U(NN3 )(OBut )(OPh)].
of the amido complexes varies with the steric bulk of the The reaction of UO2 Cl4 2 with the lithium salt of tren leads
ligand. With larger groups, for example, phenyl and pseudo- to the formation of a UV /UVI dinuclear trianion, [UO(2 -
tetrahedral, monomeric complexes result, while with smaller NCH2 CH2 N(CH2 CH2 NSiBut Me2 )2 )]2 .34 The formation of
alkyl groups, dimeric complexes with a trigonal bipyramidal this anion is complex due to the activation of both the uranyl
geometry predominate (27). Cationic complexes have also unit and the tren ligand. The structure for this complex consists
been stabilized with amido ligands, for example, the pseudo- of capped trigonal bipyramid uranium atoms. The tren ligand
octahedral [U(N(C2 H5 )2 )3 (THF)3 ]B(C6 H5 )4 (28).2426 binds through the amine and two of the amido linkages with
the third becoming an imido ligand. The remaining oxygen
atoms complete the coordination sphere as a terminal ligand.
Et2N Et2 NEt2 NEt2
N THF NEt2
Et2N An NEt2 U Hexavalent. The majority of An(VI) coordination chem-
N THF THF
Et2N Et2 NEt
2 NEt2 istry with N-donors has been explored with the uranyl
cation, UO2 2+ . Stable adducts with the ligands discussed
(27) (28)
in the tri- and tetravalent complexes have been described,
for example, UO2 X2 Ln (X = halide, OR, NO3 , RCO2 ). The
As with the case of the trivalent actinides, the tren, coordination numbers observed for these complexes are typ-
trisamidoamine (NN3 ), ligand has been used to stabilize AnIV ically 6, 7, or 8 with octahedral, pentagonal bipyramidal, or
complexes. The preparation of [An(NN3 )Cl]2 is accomplished hexagonal bipyramidal geometries, respectively. Neutral and
by the reaction of the trilithium salt of NN3 with AnCl4 anionic thiocyanates have also been isolated, for example
(An = Th, U).27 The chloride ligand can be exchanged using [UO2 (NCS)x ]2x yH2 O (x = 2 5).
metathetical reactions to form An(NN3 )X (X = Br, I, NR2 , A unique amido complex of UO2 2+ has recently
OR). Anionic complexes, An(NN3 )XX (X = OR, X = OR ) been reported, [UO2 (N(SiMe3 )2 )3 ] (29).35 This anion has
can also be formed by addition of alkoxide salts to the neutral a uranium center with a rarely observed coordination
species.28 Complexes of AnIV with diamidoamine ligands number of 5 in a trigonal bipyramidal geometry. This
have also been studied.29 complex was synthesized by protonolysis of the dian-
Polypyrazol-1-yl borate coordination with AnIV also results ion, [UO2 (N(SiMe3 )2 )4 ]2 (30) or through a reaction of
in stable complexes. The fully characterized complexes UO2 Cl2 (THF)2 with three equivalents of K[N(SiMe3 )2 ]. The
are typically of the form, AnCl2 L2 (L = HBpz3 , Ph2 Bpz2 , crystal structure of this anion revealed long U=O bonds
Bpz4 )30,31 and AnL4 (L = H2 Bpz2 , HBpz3 ). (1.80 A) and relatively short U N bonds (2.31 A).
Another unique N-donor ligand is Fe(CN)6 3/2 . The Homoleptic UVI amido complexes are also known.
ferrocyanide ion has been found to complex with AnIV U(NMe2 )6 is synthesized by a two-electron oxidation of
20 ACTINIDES: INORGANIC & COORDINATION CHEMISTRY
O
O 2 These ligands have been proposed as actinide sequestering
N(SiMe3)2 (Me3Si)2N N(SiMe3)2 agents.
(Me3Si)2N U U
N(SiMe3)2 (Me3Si)2N N(SiMe3)2
O O
8.5 Oxygen-containing Organics
(29) (30)
The actinides have a high degree of specificity for
neutral and anionic oxygen-containing organic molecules. The
the tetravalent anion [U(NMe2 )6 ]2 . The complex has an actinide complexes with O-donor ligands that are most widely
octahedral geometry and slowly decomposes over several studied include alkoxides, aryloxides amide, carboxylates, and
hours. oxalates. Complexes with alcohols, ethers, esters, ketones,
aldehydes, ketoenolates, and carbamates have also been
8.3 Phosphorus Donors reported.
RO R OR
Pu O OR
8.4 Oxygen Donors O
O O Th Th
RO O
A wide variety of O-donors have been used to complex RO R OR
uranium. The predominate oxidation states are IV and VI;
however, complexes with An(III) and An(V) are also known.
The majority of the complexes have coordination numbers (31) (32)
of 6 to 12, depending mostly on the steric bulk of the R
RO O OR
ancillary ligands. Owing to the prevalence of O-donating RO OR
R
ligands in natural systems, that is, aquo, hydroxide, carbonate, U O U
phosphate, carboxylate, and catecholate, understanding the O
RO OR
complexation of the actinides is important to environmental, U
waste processing and storage, and bioinorganic chemistry.
Some of the other O-donating ligands that have been studied RO OR
are crown ethers, Schiff bases, polyglycols, and cryptands. (33)
ACTINIDES: INORGANIC & COORDINATION CHEMISTRY 21
The consequent increase in the nuclear charge and reduction of to give pure metals at the cathode. Pyrochemistry is currently
the shielding of the 6d- and 7s-electrons lead to a contraction being investigated as an alternative to the aqueous-based
of the atomic radius, similar to that previously discussed for separation methods for nuclear fuel reprocessing since
the ionic radius. In Am and Cm, the 5f-electrons are localized pure streams of Pu can be avoided, thereby reducing
in the core, which causes an expansion of the atomic radius. proliferation risks. All actinides in elemental form are
The differences in localization of f-electrons between light lustrous silvery dense metals. Only Th has a rather
and heavy actinides are also illustrated by their different high melting point, and both Th and Np have high
superconductive and magnetic behavior. The Th, Pa, and Am boiling points. The other actinides can be purified by
metals are superconductors (Tc of 1.37, 0.42, and 0.79 K, volatilization.
respectively), whereas the heavier actinide metals are not The reactivity of the actinide metals is in line with other
superconductors but have larger magnetic moments at low electropositive highly reactive metals. In air, the actinides
temperatures. are rapidly covered with an oxide film. For Pu, the film has
The production of the light actinide metals is usually two distinct layers, PuO2 on the surface and Pu2 O3 on the
accomplished through the reduction of tri- or tetrafluorides subsurface. The relative quantity of each of these layers is
with an electropositive metal, for example, Ca, Zn, or Mg. dependent on the quantity of oxygen in the atmosphere. The
The heavy actinides are typically made through the direct metals also react with metalloids and nonmetals to form a
reduction of oxide phases. An alternative method to access number of solid-state stoichiometric and nonstoichiometric
the actinide metals is through pyrochemical methods. In this compounds. The following sections detail many of the
technique, actinides in high-temperature molten salts, for products from direct interaction of the actinide metals with
example, NaCl-KCl or LiCl-KCl eutectics, are electrolyzed other elements.
ACTINIDES: INORGANIC & COORDINATION CHEMISTRY 23
9.2 Oxides the orange -UO3 being the most important and having a
density of 7.80 g cm3 . The predominant method for synthe-
The oxides of the actinides are some of the most prevalent sizing UO3 is by thermal decomposition of UVI compounds in
and technologically important binary actinide compounds the presence of O2 . While most actinide oxides are thermally
known. The oxides of thorium, uranium, and plutonium are stable with high melting points, -UO3 decomposes at 650 C.
used throughout the nuclear fuel cycle and, for many of Hyper- and hypostoichiometric, UO2+x and UO2x ,
the actinides, are the stable phase in the environment. The respectively, are also known and have been analyzed by
oxides can be quite complex, forming nonstoichiometric and
X-ray crystallography. In the case of the UO2+x , extra oxygen
polymorphic materials. Anionic oxides of the actinides can
atoms occupy central lattice holes in the normal UO2 structure.
also be formed, for example, AnO4 2 , An2 O7 2 , AnO4 ,
The anhydrous oxide phases for Np consist of the
and so on. The focus of this section will be on the
tetravalent NpO2 and pentavalent Np2 O5 . A hydrated form
predominant or technologically relevant binary oxide phases.
of a hexavalent neptunium oxide has also been characterized.
A complete summary of the properties and crystal structure
The neptunium dioxide has an apple green color and can
data for actinide oxides can be obtained from Kirk Othmer
be synthesized by burning the metal in an atmosphere of
Encyclopedia of Chemical Technology, 4th Edition: Actinides
O2 . The density of NpO2 is 11.14 g cm3 . Np2 O5 is a
and Transactinides, Wiley-Interscience, NY, 1999.
dark brown solid that crystallizes in a monoclinic space
The thorium oxide system is dominated by ThO2 . The
group. The primary synthetic routes to obtain dineptunium
dioxide can be synthesized by burning a number of thorium
pentaoxide include thermal decomposition of NpV compounds
compounds, including hydroxides, oxalates, carbonates, and
or high-temperature ignition of the metal. The synthesis
so on. The ThO2 crystallizes in the cubic fluorite structure.
of the hexavalent neptunium oxide, NpO3 xH2 O, requires
ThO2 is very heat resistant as are all of the actinide oxides and
melts at 3390 C, which is the highest for any known metal strongly oxidizing conditions. The most efficient synthetic
oxide. route consists of reacting NpO2 with O3 in a high-temperature
Protactinium oxides can be stabilized in the tetravalent molten salt.
and pentavalent state. The most stable oxide phase obtained The plutonium oxygen phase diagram is complex. The two
by the burning of metal or protactinium compounds is the most important oxides of plutonium are the dioxide, PuO2 , and
white pentoxide, Pa2 O5 . The structure of the pentoxide the sesquioxide, Pu2 O3 . PuO2 is used in the nuclear fuel cycle
is related to fluorite and has cubic symmetry. PaO2 with the fabrication of MOX in either the recycle of spent
is a black solid that crystallizes in the cubic fluorite nuclear fuel or the destruction of plutonium from nuclear
structure. weapons. Having a fluorite structure, the yellow brown to
Numerous oxide phases of uranium have been character- green PuO2 has a density of 11.46 g cm3 and a melting point
ized, including uranium oxide, UO, UO2 , U4 O9 , U3 O7 , U3 O8 , of 2400 C. Pu2 O3 is a black solid with a hexagonal structure
UO3 ; hydrated species such as UO3xH2 O and the peroxo com- similar to the La2 O3 .
plex, UO4 xH2 O; and anionic uranates including [U2 O7 ]2 Both of these oxides are present on nearly any piece of
and [U4 O13 ]2 . The most important phases for the nuclear plutonium metal that has undergone some corrosion. Under
fuel cycle are UO2 , U3 O8 , and UO3 . UO2 is a brown to black normal conditions, the outside surface of Pu contains PuO2 ,
solid that has a melting point of 2875 C. UO2 may be synthe- while the sesquioxide forms between the PuO2 layer and the
sized through a variety of mechanisms, including (i) oxidation metal. The relative amount of these phases is dictated by the
of uranium metal, (ii) reduction of higher valent oxides, partial pressure of oxygen in the atmosphere.
(iii) thermal decomposition of uranyl uranates, (iv) oxidation Obtaining pure and well-ordered PuO2 is difficult. The
or reduction of uranium halides, (v) decarboxylation of ura- presence of hypo- and hyperstoichiometric compounds,
nium compounds of carbonic acids, (vi) hydrometallurgical PuO2x and PuO2+x , respectively, pervades nearly any
preparation, and (vii) electrolysis of uranium halides. As with synthetic technique. In recent years, interest in the study
all of the actinide dioxides, it has a cubic fluorite structure and of the hyperstoichiometric, PuO2+x , (x < 0.27) oxide phases
significantly high density at 10.95 g cm3 . U3 O8 is a mixed has increased.4750 Through the use of a variety of techniques,
valent oxide, containing UIV and UVI . Two modifications of it has been determined that PuV is present in the crystal lattice
U3 O8 are known both having a black-green color and crys- as the oxygen content increases. This finding was originally
tallizing in an orthorhombic structure. The density of U3 O8 thought to have a significant impact on the modeling of
at 8.16 to 8.41 g cm3 is significantly less than the dioxide. nuclear waste repositories due to the increase in solubility of
This property is problematic in nuclear fuels. During the PuV species in the environment. However, all of the models
burning of UO2 nuclear fuel, the presence of O2 within the were based on solubility studies with PuO2 that inevitably
fuel pins causes the formation of U3 O8 . Owing to the nearly had hyperstoichiometric oxide phases present. As a result, the
20% change in the density, any significant buildup of U3 O8 published solubility data already represent the bulk solubility
will cause swelling and eventual cracking of the fuel pellet. of plutonium oxides, including the PuV species in PuO2+x .
UO3 is the only well-characterized hexavalent actinide oxide. For the actinide elements heavier than Pu, the predominant
Six different modifications are known for the trioxide with phases that have been isolated are An2 O3 and AnO2 .
24 ACTINIDES: INORGANIC & COORDINATION CHEMISTRY
9.3 Nitrides dicarbide melts at 2475 C and boils at 4370 C (760 mm Hg).
The densities of the uranium carbide series are 13.60 g cm3
Actinide nitrides are known for Th through Cm. All of the for UC, 12.85 g cm3 for U2 C3 , and 11.69 g cm3 for UC2 .
nitrides are high melting compounds with melting points Techniques for the synthesis include the reduction of AnO2
of 2630 C, 2560 C, and 2580 C for Th, Np, and Pu, with CO2 and the direct interaction of uranium and carbon
respectively. The actinide nitrides can decompose to give N2 . under highly exothermic conditions. The crystal structure
Thorium, uranium, and plutonium nitrides are well known and of AnC is a face-centered cubic NaCl-type lattice, identical
can be used as nuclear fuels. Fuels of this type, especially to that of UN. The sesquicarbides crystallize with a body-
uranium and mixed uranium plutonium nitrides, can be used centered cubic Pu2 C3 -type structure. Multiple modifications
in lead-cooled fast reactors, which have been proposed as of the AnC2 are known, for example, -phase UC2 has a
a possible next-generation nuclear reactor and for use in body-centered tetragonal CaC2 -type structure and the -phase
deep-sea research vehicles. crystallizes in a face-centered cubic KCN-type lattice. Most
Two stoichiometric phases of thorium nitrides have been of the carbides are sensitive to oxidation by air.
investigated: ThN and Th3 N4 . ThN is a superconductor with In order to be used as nuclear fuel, carbide microspheres
a relatively low Tc . Both of these phases can be made by are required. These microspheres have been fabricated by a
high-temperature reactions of thorium metal with N2 . An carbothermic reduction of UO3 and elemental carbon to form
alternative synthetic route to Th3 N4 involves the reaction of UC. In addition to these uses, the carbides are also precursors
thorium metal with NH3 to form Th(NH)2 , which upon further for uranium nitride based fuels.
heating degrades to Th2 N2 (NH) and finally to Th3 N4 .
For uranium, three nitrides of exact stoichiometry are
known: UN, U2 N3 , and U4 N7 . As was the case with the 9.5 Hydrides
oxides, nonstoichiometric complexes can also be synthesized Actinide metals react with hydrogen at elevated tempera-
to be of the form, U2 N3+x , where the N/U ratio ranges from tures to yield a number of hydride phases with compositions
1.64 to 1.84. The brown mononitride, which is the only resembling AnH2 and AnH3 . The dihydrides are known for
nitride complex stable above 1300 C, melts at 2600 C, and Ac, Th, and Np Bk and the trihydrides have been isolated
has a density of 14.31 g cm3 . The uranium nitrides can be for Pa Bk. Thorium forms a unique hydride phase with the
made by direct interaction of the elements. Some of the other formula Th4 H15 . This compound is a superconductor with
routes to access the nitrides include: uranium metal under a Tc between 7.5 and 8 K. It is interesting to note that the
static NH3 at 300 to 350 C to yield U2 N3 , uranium metal superconductivity of thorium metal is destroyed by the pri-
or uranium carbides with NH3 or N2 at 600 to 900 C to mary hydrogenation, for example, formation of ThH2 . This
produce U2 N3+x , uranium carbide fuels reacted with N2 /H2 behavior of alternating superconductivity could be attributed
to form UN, and a self-propagating metathetical reaction. to the presence of two types of hydrogen atoms in the Th4 H15
The structures of some of the nitrides have been determined structure.
with the mononitride having a face-centered cubic NaCl-type The AnH2 (An = Ac, Np Bk) have the fluorite structure.
structure. The sesquinitride complex has two modifications: ThH2 is unique in that it has tetragonal symmetry. In -UH3 ,
the -phase is found with a body-centered cubic Mn2 O3 -type the metal atoms have a coordination number of 12 and the
structure, while the high-temperature -phase crystallizes in a H atoms occupy tetrahedral intersites. For the other AnH3
hexagonal Mn2 O3 -type structure. (An = Np Bk), the crystals have a trigonal structure.
The studies on the neptunium nitride system are somewhat The hydrogenation reaction of the actinides is a reversible
limited with the mononitride, NpN, being the predominant process. By heating the hydrides to high temperatures, H2
phase. PuN is also the only known compound in the plutonium gas is driven off, leaving the pure metal. This process has
series. The AnN (An = Np, Pu) has been synthesized by been adopted in the dismantling of plutonium pits from excess
reaction of an actinide hydride with NH3 at high temperatures. nuclear weapons.51 In this process, the plutonium part is
reacted with H2 gas, which forms a powdered plutonium
hydride. The powder is collected and heated past the melting
9.4 Carbides
point of plutonium to drive off the dihydrogen gas and leave
Actinide carbides are also a potential nuclear fuel. The a Pu ingot.
typical reactors that can be fueled by carbides are thermionic,
used for space power and propulsion systems, and high- 9.6 Borohydrides
temperature gas-cooled reactors. Three basic carbides have
been isolated for the light actinides, AnC, An2 C3 , and AnC2 . The borohydrides of the tetravalent actinides can be
Ternary carbides formed from transition metals and the light prepared through the reaction of the tetrafluoride with
actinides have also been studied. Uranium carbides are all Al(BH4 )3 . The products of this reaction are An(BH4 )4 and
dark gray solids with a metallic luster. The melting points of AlF2 (BH4 ).52 The uranium complex is polymeric in the solid
UC and U2 C3 are 2400 and 2417 C, respectively, and the state and is similar to the Zr and Hf analogs. The metal center is
ACTINIDES: INORGANIC & COORDINATION CHEMISTRY 25
bound to 14 hydrogen atoms from two tridentate BH4 ligands 6, respectively. The oxidation state of the actinides in
and four bridging bidentate BH4 ligands. These complexes monochalcogenides has metallic conductivity but U2 S3 is a
represent the highest coordination number observed for an semimetal, while the Np and Pu analogs are ionic compounds.
actinide species. Recently, the first quaternary plutonium metal thiophos-
phates of the form KPu(PS4 )2 and MPuP2 S7 (M = K+ , Rb+ ,
Cs+ ) were prepared using reactive flux methods.54,55 The
9.7 Borides structure of KPu(PS4 )2 shows an eight-coordinate bicapped
trional prism geometry about the Pu center. The polyhedra are
A number of borides of composition AnB2 , AnB4 , AnB6 , linked through edge-sharing and thiophosphate tetrahedral.
and AnB12 are known. The AnB6 and AnB12 phases have The MPuP2 S7 contains P2 S7 4 corner-shared bitetrahedral
cubic structures like CsCl and NaCl, respectively. All of the ligands.
borides are resistant to the action of H2 SO4 , HCl, and HF, but The first polychalcogenide complex, K4 USe8 , was obtained
readily dissolve in HNO3 H2 O2 . by a solid-state reaction.56 It has a molecular structure
Recently, a novel synthesis of UB4 has been accomplished with a distorted dodecahedral anion, [U(Se2 )4 ]4 , which is
through a solid-state metathesis reaction.53 The reaction is isostructural with the known peroxoanions [M(O2 )4 ]n , where
performed at 850 C by mixing UCl4 with 2 equivalents M = V, Nb, Ta, Cr (n = 3) or Mo, W (n = 2). Recently, two
of MgB. The resulting UB4 product can be purified by washing additional uranium selenides have been synthesized, MU2 Se6
with H2 O. (M = K+ , Cs+ ), using a reactive flux method. The oxidation
state of the uranium in these compounds was found to be
9.8 Silicides tetravalent. The selenium has two distinct oxidation states,
Se2 and one similar to a polyselenide network.
The silicides of the actinides have not been widely New solid-state compounds of phosphoselenates also have
characterized. A uranium silicide of the form U3 Si2 has been synthesized by reaction of Th and P in a reactive flux
received the maximum amount of study owing to its use of K2 Se4 /Se or Cs2 Se3 /Se at high temperatures.57,58 For the
as a dispersion fuel in research reactors. Another common potassium system, the -K2 ThP3 Se9 was crystallographically
phase observed for actinide silicides is AnSi2 . One of the characterized and showed the Th atoms being coordinated
common synthetic routes to the silicides is the reaction of to nine Se atoms from phosphoselenate ligands. The
actinide fluorides, for example, AnF4 , with elemental Si at coordination geometry is best described as a distorted
high temperatures. One of the thermodynamic driving forces tricapped trigonal prism. In the Cs system, the compound
for this reaction is the release of SiF4 . Cs4 Th4 P4 Se26 was isolated.59,60 The molecule is best described
as [Cs2 Th2 (P2 Se9 )(Se2 )2 ]2 with the P2 Se9 6 anion having a
linear Se Se Se backbone.
9.9 Pnictides
Five pnictide phases have been identified: An4 X3 , AnX, 9.11 Halides
An3 X4 , An2 X3 , and An4 X3 . The best studied of the pnictides
outside of the nitrides are the phosphides. Some interesting Actinide halide compounds have found extensive utility
properties are observed for the phosphides; for example, Th3P4 in the processing of actinide materials as well as for starting
is a semiconductor. Most of the actinide pnictides are prepared materials for synthetic inorganic and coordination chemistry,
by direct interaction of the elements at high temperatures. for example, AnXm (THF)n (m = 3, 4, 5). The actinide
Monopnictides have been obtained from U through Cf for Sb. halides can be made in a variety of oxidation states (III VI)
They are produced by the direct interaction of the elements at through room-temperature and high-temperature techniques.
elevated temperatures. The trihalides, AnX3 , are stable for all of the actinides except
Th and Pa. As a result of the important industrial applications
of binary fluorides and chlorides, the majority of the halide
9.10 Chalcogenides discussion focuses on the binary systems. A selected listing of
physical constants for the binary uranium halides is provided
The interaction of the actinides or of their hydrides in Table 6. The bond distances for ThX4 and UX4 compounds
with chalcogens or H2 X, respectively, give a number are given in Table 7.
of nonstoichiometric phases with a composition close to Some of the general trends among the actinide halides are
AnX, An2 X3 , AnX2 , An2 X5 , or AnX3 . Their thermal as follows:
stability decreases in the order S > Se > Te. The magnetic
susceptibility and Mossbauer spectroscopy show that the Stability of the halide is dependent on the redox chemistry
latter compounds may be formulated as [An3+ ]2 (S2 )2 (S- of actinides (PuIV is reduced by Cl , Br , and I ).
S)2 , [An4+ ]2 (S2 )3 (S-S)2 , and [An4+ ](S2 )(S-S)2 . These Fluoride stabilizes the higher oxidation states of the
compounds have coordination numbers of 8, 10, and actinides.
26 ACTINIDES: INORGANIC & COORDINATION CHEMISTRY
Table 6 Physical constants for selected uranium halides Trivalent. The actinide trifluorides have a structure that
is isomorphous with LaF3 , in which each metal has a basic
Melting Boiling tricapped triganol prismatic geometry with an additional
Density, point, point,
Compound g mL1
C
C two fluoride ions at a significantly longer distance. The
trifluorides tend to be insoluble in H2 O but quite soluble
UF6 4.68 64.5 64.8 56.2765 in strong acids, that is, nitric, hot sulfuric, and perchloric.
UF4 6.70 960 For the actinides with very stable trivalent oxidation states,
UF3 >1000
Ucl5 3.81 >300 for example heavy actinides, the synthetic routes to form
Ucl4 4.87 590 792760 the AnF3 are straightforward (equations 3 5). For the light
Ucl3 5.44 842 actinides, the isolation of the trifluorides requires the addition
Ubr4 5.35 516 792760 of a reducing agent, for example H2 (equations 6 7).
Ubr3 6.53 730 Volatile
UI4 5.6 506 759760
HF
Ac(OH)3
AcF3 (3)
700 C
HF
Table 7 Bond distances for thorium and uranium halides, ThX4 and AmO2 AmF3 (4)
UX4
F dry
F Cl Br I Cm3+
(aq) CmF3 xH2 O AmF3 (5)
P 2 O5
Th-Xgas (A) 2.14 2.58 2.72 HF/H2
Th-Xsolid (A) 2.34 2.88 3.00 3.21 MO2
MF3 (M = Np, Pu) (6)
500 C
U-Xterminal (A) 2.28 2.71 2.61 2.92
U-Xbridging (A) 2.88 3.10 Al or UH3 or H2
UF4
UF3 (7)
900 C
Table 8 Coordination numbers and geometries for UX4 and Un Tetravalent. The tetrafluorides of the actinides are
bromides typically synthesized through the reaction of HF or Freon
with the actinide metals, oxides, or hydrides. Since the highest
UX4 F Cl Br I
possible oxidation state for Th is the tetravalent state, F2
CN 8 8 7 6 can be used to synthesize ThF4 . The solid-state structure
Geometry Square Dodeca- Pentagonal Octa- of the light actinide tetrafluorides consists of polymers that
anti- hedron bipyramid hedral
are created through bridging fluoride ions. The geometry
prism
around the metal center is a distorted square antiprism. In
Un -bromides V IV III
CN 6 7 9 general, the tetrafluorides are soluble in strong acids and
Geometry Octa- Pentagaonal Tricapped bases, insoluble in dilute acids and bases, and slightly soluble
hedral bipyramid trigonal in cold water. Equations (8 10) provide some examples of
prism potential synthetic routes.
HF
Umetal UF4 (8)
Coordination numbers decrease with increasing size of the
higher temperatures has eight-coordinate uranium atoms in an Tetravalent. The tetrachlorides AnCl4 are stable for all
irregular geometry. of the light actinides, Th Pu. The structure for AnCl4
(An = Th Np) have a dodecahedral geometry of the chlorine
HF/H2 F2
atoms about a central actinide metal center. The methods used
Pa2 O5 PaF4
PaF5 (11)
700 C to synthesize the tetrachlorides are dependent on the actinide
KrF2 /HF of interest. For Th, the direct interaction of the metal with Cl2
NpF4
NpF5 (12) is the most direct method. PaCl4 can be made by reduction
500 C
of PaCl5 with hydrogen or aluminum at high temperatures.
Hexavalent. Uranium hexafluoride, UF6 , is one of the Uranium tetrachloride is a dark green solid that can be prepared
best-studied uranium compounds in existence due to its in multiple ways. The most efficient synthesis involves the
importance for uranium isotope separation and large-scale reaction of UO3 with boiling hexachloropropene. UH3 can
production (70 000 tons per year). All of the actinide also be treated with Cl2 to give UCl4 . The red NpCl4 is
hexafluorides are extremely corrosive white (U), orange (Np), predominantly made by reacting CCl4 at high temperatures.
or dark brown (Pu) crystalline solids, which sublime with ease The reaction of PuCl3 with Cl2 results in an equilibrium
at room temperature and atmospheric pressure. The synthetic between the tri- and tetrachloride.
routes into the hexafluorides are given in equation (13).
The volatility of the hexafluorides increases in the order
Pu < Np < U in the liquid state and Pu < U < Np in the Pentavalent. Actinide pentachlorides are limited to PaCl5
solid state. UF6 is soluble in H2 O, CCl4 , and other chlorinated and UCl5 . PaCl5 has a chain-type structure with seven-
hydrocarbons, is insoluble in CS2 , and decomposes in alcohols chloride ions bound to each metal center. UCl5 consists of an
and ethers. The oxidative power of the actinide hexafluorides edge-sharing bioctahedral dimer, U2 Cl10 . The protactinium
are in line with the transition metal hexafluorides and the order pentachloride is most easily accessed through a high-
of reactivity is as follows: PuF6 > NpF6 > UF6 > MoF6 > temperature reaction of Pa2 O5 with a mixture of C, Cl2 ,
WF6 . The UF6 molecule can also react with metal fluorides to and CCl4 . UCl5 is a reddish brown solid that can be prepared
form UF7 and UF8 2 . The same reactivity is not observed by reaction of UO3 under flowing CCl4 . While this procedure
for the Np and Pu analogs. can be used to make UCl4 , the reaction can be controlled to
stop at UV by lowering the temperature. The direct oxidation of
F2 UCl4 by Cl2 can also be used to synthesize the pentachloride.
Anmetal or AnO2 AnF6 (13)
500 C The pentachloride decomposes in H2 O and acid, is soluble in
anhydrous alcohols, and insoluble in benzene and ethers.
9.11.2 Chlorides
Trivalent. The trichlorides, AnCl3 , are stable across Hexavalent. The best-studied actinide hexachloride is
the series, and two structure types have been observed: uranium hexachloride, UCl6 . This compound is prepared by
nine-coordinate UCl3 (tricapped trigonal prism) and eight- chlorination of UCl4 with SbCl5 . The disproportionation of
coordinate PuBr3 (bicapped trigonal prism). The early UCl5 to form UCl4 and UCl6 provides a second route to
actinides favor the former structure type, while Bk and Cr access the hexachloride. An alternative preparative approach
are found in the latter. A variety of synthetic routes can be is the disproportionation of UCl5 to UCl4 and UCl6 . The
used to access the trihalides, including metathesis, reduction, hexachloride is isostructural with the hexafluoride, being
oxidation, and so on (equations 14 19). monomeric with an octahedral arrangement of the chlorine
atoms around the uranium center.
NH4 Cl or CCl4
Ac(OH)3 AcCl3 (14)
250 C or 500 C
NH4 Cl
9.11.3 Bromides and Iodides
AmCl3 xH2 O
AmCl3 (15)
250 C
Trivalent. Owing to the weakly oxidizing power of
HCl bromine and iodine, the majority of the isolated compounds
M2 O3 MCl3 (M = Cm, Es) (16)
400 600 C consist of trivalent actinides, for example, AnX3 (X = Br, I).
Cl2 The tribromides AnBr3 have been isolated for An = Ac Bk.
Pumetal
PuCl3 (17) The light actinides Ac Np have the nine-coordinate UCl3
450 C
structure, while Pu, Am, and Cm are found with an eight-
HCl/H2
UH3 UCl3 (18)
coordinate bicapped trigonal prismatic geometry. With the
350 C decreasing ionic radius due to the actinide contraction, the Bk
H2 analog crystallizes with a six-coordinate structure. The general
NpCl4
NpCl3 (19) synthetic methods to synthesize the actinide tribromides are
600 C
28 ACTINIDES: INORGANIC & COORDINATION CHEMISTRY
HBr
Nearly all of the halides of the actinides can undergo partial
M2 O3 MBr3 (M = Cm, Cf ) (20) oxidation or hydrolysis to form actinide oxyhalide compounds
600 800 C
and complexes. Actinide tetrahalides react with dioxygen or
Br2 other oxygen donors to give AnOX2 . Protactinium halides
Umetal
UBr3 (21)
500 C undergo a number of oxidation reactions to form compounds of
HBr the form PaO2 F, PaOBr3 , PaOI, and PaO2 I. The predominant
UH3 UBr3 (22) uranium oxyhalides are of the form UOXn (n = 2, 3)
solvents for actinide separations, the large electrochemical dust formation, face masks, constant ventilation, and glove
windows allow for the use of pyrochemical methods to boxes. Finely divided actinide metals, some alloys, and the
electroplate actinide metals at room temperature. The current hydrides are pyrophoric; therefore, such materials should be
pyroprocessing technologies for reprocessing spent nuclear handled in an inert atmosphere glove box.
fuel require the use of high-temperature molten NaCl/KCl Isotopes that emit fairly strong -radiation, should be
eutectics. handled in a hot cell; 238 Pu, 241 Am, 243 Am and similar isotopes
should be handled in glove boxes; 237 Np, 239 Pu, 242 Pu, 244 Pu,
Hydrothermal Synthesis. Hydrothermal synthesis68,69 and 248 Cm can be handled in a fume hood or glove box;
235
and reactive fluxes have been increasingly used as a method U and 238 U can be handled on the bench top or in a fume
for synthetic actinide chemistry. Unique phases of actinide hood because of their lower radiation fields. The laboratory
selenites, tellurites, iodates70 and periodates71 have all been should be equipped as an -laboratory. In the handling of the
synthesized under hydrothermal reaction conditions. New actinides, as in the case of all radionuclides, radioactivity due
compounds and phases of oxyfluorides, phosphates, and sul- to the progeny, such as Th, Ra, Rn, and so on, should be
fates using organic templates also have been synthesized with considered, as should alternative radiation-generating decay
hydrothermal methods.7274 paths, for example, -n reaction from uranium fluorides.
Large quantities of fissile isotopes, 233 U and 235 U, 237 Np,
239
Pu, and so on, should be handled and stored appropriately to
avoid a critical hazard. Clear and relatively simple precautions,
such as dividing quantities so that the minimum critical mass
10 HEALTH AND SAFETY FACTORS
is avoided, following administrative controls, using neutron
poisons, and avoiding critical configurations (or shapes), must
10.1 Exposure and Health Effects be followed to prevent an extremely treacherous explosion.
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ACTINIDES: INORGANIC & COORDINATION CHEMISTRY 31
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Actinides: Organometallic The large size of actinide ions permits coordination
numbers and attendant polyhedra that are uncommon among
Chemistry the transition elements. For the same set of ligands, a 5f-
element ion will be more coordinatively unsaturated than
a d-element ion. The availability of 5f valence orbitals
Carol J. Burns, David L. Clark & Alfred P. Sattelberger also suggests a greater variety of metal ligand binding
Los Alamos National Laboratory, Los Alamos, NM, USA possibilities, smaller ligand field stabilization energies, smaller
energy barriers to intra- and intermolecular ligand exchange,
and a greater degree of ionic character in metal ligand
bonding that leads to more electrophilic metal centers and
1 Introduction 1 correspondingly more nucleophilic ligand centers. Modern
2 Cyclopentadienyl and Substituted Cyclopentadienyl organoactinide chemistry is now characterized by the existence
Complexes 1 not only of actinide analogs to many classes of d-transition
3 Cyclooctatetraene Complexes 9 metal complexes, but increasingly common reports of
4 Allyl, Pentadienyl, and Related Complexes 11 compounds and types of reactions unique to the actinide
5 Arene Complexes 12 series. We will touch on these points throughout this chapter.
6 Other Carbocyclic Ligands 13 The first actinide organometallic complex, red-brown
7 Alkyl Complexes 14 (C5 H5 )3 UCl, was prepared and characterized by Reynolds
8 Hydride Complexes 18 and Wilkinson in 19561 or shortly after the discovery
9 Carbonyl Complexes 18
of ferrocene (see Ferrocene), (C5 H5 )2 Fe. However, it was
10 Phosphoylide Complexes 19
not until the preparation and structural characterization of
11 Organoactinide Surface Chemistry and Catalysis 19
bis(cyclooctatetraenyl)uranium, (C8 H8 )2 U (uranocene, see
12 Electronic Structure and Bonding 21
Uranocene) in 19682 and the isolation and characterization
13 Related Articles 23
of uranium alkyls (see Alkyl Complexes) in 19733 that the
14 References 23
field developed momentum. The purpose of this chapter is to
provide an overview of organoactinide chemistry that reflects
historical as well as recent developments and achievements
in the field; it is not meant to be an exhaustive review of
the primary literature. More detailed discussion, background
1 INTRODUCTION material, and extensive references to the literature can be
found in several excellent reviews.410
The past 50 years have witnessed many important Not every actinide element has known or well-developed
and exciting developments in the chemistry of transition organometallic chemistry. By far the most research has been
metal complexes containing hydrocarbon-based ligands (often done on thorium and uranium compounds, a consequence
referred to as hydrocarbyl ligands, see Hydrocarbyl). of favorable isotope-specific nuclear properties and, at least
Transition metal organometallic chemistry is a vibrant and until recently, the commercial availability of key starting
evolving field, one stimulated by many factors including materials such as 232 Th metal, anhydrous 232 ThCl4 , U metal,
inorganic and organic chemists interests in new synthetic, and anhydrous 238 UCl4 .11 Thorium chemistry is dominated
mechanistic, and structural chemistry, materials chemistry, by the +4 oxidation state and has some similarities to the
nanoscience and nanotechnology, and homogeneous and chemistry of the heavier group 4 metals. For uranium, one
heterogeneous catalysis. Despite a few early reports on the can access oxidation states from +3 to +6 in organic media.
synthesis of uranium and thorium cyclopentadienyl complexes Although there are some similarities to the chemistry of the
(see below), actinide or 5f-element organometallic chemistry heavier group 6 elements, for example, tungsten, there are also
is a field of more recent vintage. All known isotopes of these some remarkable differences made possible by the availability
elements are radioactive, with half-lives varying from seconds of the 5f valence orbitals.
to billions of years. Radioactive decay, and the attendant high
costs of equipping laboratories for working with, monitoring,
and disposing of radionuclides, represents an activation barrier
(for the transuranic elements, a very significant one) for 2 CYCLOPENTADIENYL AND SUBSTITUTED
organoactinide research and there are relatively few academic CYCLOPENTADIENYL COMPLEXES
and national laboratories equipped to explore this area of
chemistry. It is the authors belief that there is much more Organoactinide chemistry initially developed around the
to be learned about the organometallic chemistry of the early use of the ubiquitous cyclopentadienyl ligand (see Cyclo-
actinides, that is, thorium through plutonium, particularly pentadienyl), Cp = C5 H5 , and subsequently its alkyl- and
through systematic studies of related complexes. silyl-substituted derivatives. The tetravalent oxidation state
2 ACTINIDES: ORGANOMETALLIC CHEMISTRY
dominates the cyclopentadienyl chemistry of the early bond dissociation energy in Cp4 U has been estimated from
actinides, but the number of reports on trivalent actinide thermochemical combustion data to be 247 kJ mol1 .14 The
cyclopentadienyl systems has grown steadily over the past latter may be compared to the value of 297 kJ mol1 found
decade. The literature on protactinium(IV) and tetravalent for Cp2 Fe (ferrocene, Ferrocene). Compilations of thorium
and trivalent transuranic cyclopentadienyl compounds is and uranium metal ligand bond disruption enthalpies (see
sparse, and the reaction chemistry of these compounds is Bonding Energetics of Organometallic Compounds) are
not particularly well developed. A remarkable series of available and are quite useful for interpreting and even
uranium(V) and uranium(VI) cyclopentadienyl compounds predicting the course of organoactinide reactions.15
that have no transition metal analogs are of more recent Concomitant with the development of synthetic, mech-
vintage and will be described in due course. anistic, and structural organoactinide chemistry, there has
been an ongoing debate regarding the extent of covalency in
actinide ligand bonds.8,10 It is important to emphasize that the
2.1 Cp4 An Compounds debate is usually about the degree of covalency in a particular
Tetrakis(cyclopentadienyl) actinide complexes, actinide ligand bond, rather than whether or not it exists. Most
(C5 H5 )4 An, were among the earliest organoactinide com- workers in the field agree that covalency contributes to early
plexes synthesized and can be prepared by metathesis (see actinide-ligand bonding in compounds where the formal oxi-
Metathesis) of the anhydrous tetrachlorides (AnCl4 ) with dation state of the metal is +3 or greater. There is also general
potassium cyclopentadienide (KCp) in refluxing benzene agreement that actinide-ligand interactions are predominantly
(equation 1, for An = Th, U, and Np).12 Another member ionic for late actinide organometallic compounds in which the
of this series, Cp4 Pa, formal oxidation state of the metal is +3. A discussion of cur-
rent theoretical views on this topic will be delayed until later,
C6 H6
but along the way we will cite experimental data that suggests
AnCl4 + 4KCp AnCp4 + 4KCl (1) that actinide ligand bonds have appreciable covalent charac-
ter. A comparison of the 237 Np Mossbauer spectra of Cp4 Np
and NpCl4 is one such example.16 The organometallic com-
has been synthesized in a solvent-free reaction between
pound exhibits an isomer shift that is 1.06 cm s1 higher than
protactinium tetrachloride, PaCl4 , and Cp2 Be (equation 2).12
that observed for the chloride. This difference has been taken
All of the Cp4 An compounds are sparingly soluble in organic
as an indication of substantially greater shielding of the 6s
shell in Cp4 Np and enhanced metal ligand bond covalency.
PaCl4 + 2Cp2 Be Cp4 Pa + 2BeCl2 (2)
solvents. The thorium and uranium compounds have been 2.2 Cp3 AnX Compounds
structurally characterized.13 IR spectra and X-ray powder As mentioned in the Introduction, (C5 H5 )3 UCl was the
diffraction data indicate that the other two members of the first organoactinide compound reported in the literature.
series are isostructural. The molecular structure of Cp4 U
Its preparation from UCl4 and sodium cyclopentadienide in
features a nearly tetrahedral coordination geometry as shown
tetrahydrofuran has been generalized, and most of the early
in (1), with four 5 -cyclopentadienyl ligands whose average
actinide tris(cyclopentadienyl) halides can be prepared by the
UCring distance is 2.81(2) A.
synthetic methodology outlined in equation (3).1,6 Solvents
for this reaction are generally polar organics such as THF
or DME.
DME
AnX4 + 3M Cp AnCp3 X + 3M Cl (3)
U
The X-ray structure of Cp3 UCl reveals a distorted
tetrahedral uranium coordination geometry as shown in (2)
with three 5 -Cp ligands at 2.74(1) A from the metal center and
the UCl bond (2.559(16) A) coincident with the molecular
threefold axis.17 This type of structure is essentially identical
(1)
for all Cp3 UX derivatives. A more accurate X-ray diffraction
study of tris(benzylcyclopentadienyl)uranium(IV) chloride
These UC distances are roughly 0.1 A longer than gave an average UCring distance of 2.733(1) A and a UCl
typically observed in other U(IV) cyclopentadienyl complexes distance of 2.627(2) A.18
and likely reflect the pronounced crowding associated with In contrast to the reactions of trivalent lanthanide Cp
four 5 -C5 H5 ligands about the metal center. The mean compounds (Cp3 Ln) with iron(II) chloride, Cp3 UCl does
ACTINIDES: ORGANOMETALLIC CHEMISTRY 3
Cp3UGePh3
(3)
2.3 Cp2 AnX2 Compounds for short), have been used to stabilize tetravalent thorium
and uranium ions. The complexes can be synthesized by
Complexes of general formula (C5 H5 )2 AnX2 have proven reaction of the metal tetrachlorides with either lithium or
difficult to synthesize and are prone to redistribution reactions. magnesium reagents.36 Metathetical reactions of Cp 2 UCl2
Thus, Cp2 UCl2 prepared in DME via the metathesis of or Cp 2 UCl2 with XSiMe3 (X = Br, I) or BF3 (Et2 O) provide
UCl4 with two equivalents of thallium(I) cyclopentadienide a convenient route to the other halide analogs. The molecu-
is actually a mixture of Cp3 UCl and CpUCl3 (DME).29 lar structures of (1,3-R2 C5 H3 )2 UX2 (R = SiMe3 , X = F, Cl,
Cp2 AnCl2 compounds have, in some instances, been Br; R = CMe3 , X = F, Cl) have been reported, as well as
successfully stabilized against ligand redistribution by adding the structure of [1,3-(Me3 Si)2 C5 H3 ]2 ThCl2 . With the excep-
ancillary ligands. The Cp2 ThX2 unit, for example, can tion of [Cp 2 UF(-F)]2 , all of the complexes are monomeric
be stabilized by adding the chelating alkyl phosphine in the solid state. In solution, the fluoride dimer is appar-
Me2 PCH2 CH2 PMe2 (dmpe) to form Cp2 ThX2 (dmpe) for ently in equilibrium with its mononuclear counterpart. The
X = Cl, Me (equation 6).30 Analysis of X-ray diffraction 1
H NMR chemical shifts and magnetic susceptibility data
data reveals a pseudo-octahedral coordination environment as for the two fluoride complexes indicate that the ligands pro-
shown in (4). duce significantly different electronic environments about the
uranium(IV) center.36
THF
ThCl4 (dmpe) + 2NaCp Cp2 ThCl2 (dmpe) + 2NaCl (6) In some cases where bulky cyclopentadienyl ligands are
used, it is still possible to isolate Lewis base adducts.
Two examples are Cp 2 UCl2 (pz) (pz = pyrazole)37 and [1,3-
X (Me3 Si)2 C5 H3 ]2 ThCl2 (dmpe).38 In compounds of the type
R2 Cp 2 UX2 (L), the neutral ligand L occupies the central position
P in the equatorial wedge.
Th
Metathesis routes have been used to prepare termi-
nal amido, phosphido, and thiolato complexes (equa-
P tions 8 10) from Cp 2 AnCl2 starting materials.39 For the
R2 bulky bis(trimethylsilyl)phosphido ligand, only mono substi-
X
tution occurs.
(4)
Et2 O
Cp 2 AnCl2 + 2LiNR2 Cp 2 An(NR2 )2 + 2LiCl (8)
Stabilization against redistribution has also been achieved PhCH3
through the use of sterically demanding X groups (e.g. 3 - Cp 2 ThCl2 + 2LiPPh2 Cp 2 Th(PPh2 )2 + 2LiCl (9)
BH4 ), the use of ligands capable of both - and -donation THF
Cp 2 UCl2 + 2NaSR Cp 2 U(SR)2 + 2NaCl (10)
to the actinide metal center (e.g. NEt2 ), or the use of ring-
bridged Cp ligands [Me4 C5 XC5 Me4 ]2 (X = CH2 , Me2 Si,
Toluene solutions of the thorium complex, Cp 2 Th(PPh2 )2
CH2 CH2 CH2 ).31 For example, treatment of Cp2 U(NEt2 )2 with
reacts smoothly with Pt(COD)2 in the presence of
bulky alcohols gives a variety of stable Cp2 UX2 complexes
trimethylphosphine to provide Cp 2 Th(-PPh2 )2 Pt(PMe3 ), a
(X = OC(t-Bu)3 , O-2,6-Me2 C6 H3 , etc.)32 and reaction of
complex with a thorium platinum bond. The latter can be
thorium or uranium tetrachloride with two equivalents of
regarded as a formal donor acceptor or dative bond from the
(C5 Me5 )MgCl(THF) in toluene gives stable (C5 Me5 )2 AnCl2
filled d10 shell of Pt into the empty d shell of Th.40
complexes (equation 7).33
The bis-MeC5 H4 or bis-Cp* framework is a use-
ful template for organoimido and organophosphinidene
PhCH3
AnCl4 + 2(C5 Me5 )MgCl(THF) (C5 Me5 )2 AnCl2 + 2MgCl2 (7) complexes. Comproportionation of uranium(III) and ura-
nium(V) metallocenes provides a route to dinuclear ura-
nium(IV) imido complexes (equation 11).41 The molecular
The C5 Me5 or Cp* ligand has evolved as one of the most structure of [(MeC5 H4 )2 U(NPh)]2 is depicted in (5).
widely used ligands in organoactinide chemistry owing to
the thermal stability, solubility, and crystallizability it imparts THF
to compounds. The molecular structures of Cp 2 UCl2 and (C5 H4 Me)3 U(THF) + (C5 H4 Me)3 U(NPh)
Cp 2 ThX2 (X = Cl, Br, I) have been determined.34 All of the [(C5 H4 Me)2 U]2 (-NPh)2 (11)
Cp 2 AnX2 complexes are mononuclear and members of the
pseudotetrahedral, bent metallocene (see Bent Metallocenes) Terminal organoimido complexes of uranium(IV) are
family. The analogous neptunium complex has been reported a more recent discovery. An -elimination reaction (see
from the reaction of NpCl4 with Cp*MgClTHF.35 -Elimination) was designed for the synthesis of Cp 2 U(=N-
Other substituted cyclopentadienyls, such as [1,3- 2,4,6-t-Bu3 C6 H2 ) (equation 12). The structure of Cp 2 U(=N-
(Me3 Si)2 C5 H3 ] and [1,3-(Me3 C)2 C5 H3 ] (Cp and Cp 2,4,6-t-Bu3 C6 H2 ) reveals a very short U=N distance 1.95(1) A
ACTINIDES: ORGANOMETALLIC CHEMISTRY 5
PhCH3
(5)
CPh2
42 N
and a large UNCipso angle of 162.3(10) .
N (15)
Cp*2U
Cp 2 UMe2 + H2 N-t-Bu3 C6 H2 Cp 2 U(=N-t-Bu3 C6 H2 ) + 2CH4 NH
(12)
tBu
the average UO distance is 2.44(2) A. The disposition of the The molecular structure of Cp3 U(THF) features a
Cl ligands cis and trans to the cyclopentadienyl ring apparently distorted tetrahedral coordination geometry (8) with UC =
minimizes intramolecular nonbonded repulsions. Other routes 2.76 2.82 A and UO = 2.55(1) A,52 while (Me3 SiC5 H4 )3 U
to CpUX3 L2 compounds begin with the corresponding UX4 L2 (Cp 3 U) is trigonal planar.53 The trigonal geometry of
Cp 3 U is only moderately perturbed by interaction with ethyl
isocyanide to form Cp 3 U(CNEt).54
Cl THF
U
THF Cl O
Cl
U
(7)
isostructural with their early actinide analogs.4 mononuclear, end-on bonded Cp 3 U(1 -N2 ). The latter is the
first monometallic f-element dinitrogen complex.62
2AnCl3 + 3BeCp2 2AnCp3 + 3BeCl2 (An = Pu, Am, Cm, Bk, Cf)
(21)
2.6 Cp2 AnX Complexes
A useful development in the synthetic chemistry of While complexes of general formula Cp2 MX are very
trivalent actinide complexes in recent years has been the common in organolanthanide chemistry, they are relatively
development of the more soluble iodide starting materials, rare in organoactinide chemistry. Sodium amalgam or tert-
AnI3 L4 (An = U, Np, Pu; L = THF, py, DMSO, etc.).59 butyl lithium reduction of Cp 2 UX2 and Cp 2 UX2 provides
These species, generated from actinide metals and iodide dimeric [Cp 2 UX]2 or [Cp 2 UX]2 (equation 23).63 The dimers
sources (e.g. HgI2 , I2 , etc.) in coordinating solvents, are are readily cleaved in THF to give monomeric Cp 2 UX(THF)
readily soluble in organic solvents, and serve as convenient or Cp 2 UX(THF). The related compound Cp 2 UI(THF) is
precursors to a variety of trivalent actinide species. Potassium conveniently prepared by reaction of two equivalents of KCp*
reagents are preferred for reactions in THF as the metathesis with UI3 (THF)4 in THF solution (equation 24).64
by-product KI is quite insoluble in this solvent. Interestingly,
a tungsten(III) analog of UI3 (THF)4 , viz., octahedral, mer-
C6 H14
WCl3 (THF)3 , has only recently been prepared.60 It illustrates Cp 2 UX2 + t-BuLi [Cp 2 UX]2 + LiCl
the fact that actinide centers typically accommodate a larger
ligand set than their transition metal analogs. THF
Despite the common use of the pentamethylcyclopentadi-
enyl ligand in actinide and lanthanide chemistry, it is only 2Cp 2 UX(THF) (23)
recently that a tris-complex, Cp*3 An, has been prepared with THF
this ligand. It was previously thought that the large steric bulk UI3 (THF)4 + 2KCp Cp 2 UI(THF) + 2KI (24)
associated with this ligand might preclude incorporation of
three Cp* groups in the coordination sphere of an actinide
and, in fact, direct metathesis routes are not successful. The The uranium(III) complexes {[1,3-R2 C5 H3 ]2 U(-OH)}2
complex (5 -C5 Me5 )3 U was initially prepared by reaction of (R = Me3 Si or Me3 C) have been prepared by reaction of one
a trivalent hydride complex with tetramethylfulvene (equa- equivalent of water with Cp 3 U and Cp 2 UH, respectively.
tion 22).61 Since its discovery, several other routes to Cp*3 U Upon heating, these complexes undergo an unusual oxidative
elimination reaction to yield the corresponding -oxo
uranium(IV) complexes (equation 25).65 The kinetics of this
PhCH3 process has been examined, and the reaction is found to be
Cp*2UH(dmpe) + Cp*3U + dmpe (22)
intramolecular, probably
PhCH3
have been developed.61 The molecular structure is depicted in Cp 4 U2 (-OH)2 Cp 4 U2 (-O)2 + H2 (25)
(9). The average UCring bond distance in this compound
(2.858(3) A) is longer than in other crystallographically
characterized U(III) pentamethylcyclopentadienyl complexes involving a stepwise -elimination process (see -
(2.77 A), suggesting a significant degree of steric crowding. Elimination).
One of the most thoroughly investigated Cp2 AnX systems
is the chloride-bridged, trimeric complex [Cp 2 U(-Cl)]3 .66
The complex can be prepared by a number of routes, one of
which is shown in equation (26). [Cp 2 U(-Cl)]3 reacts with
a variety of Lewis bases to generate mononuclear adducts, and
will undergo metathesis reactions.
U
PhCH3 2
Cp 2 UH2 + Cp 2 UCl2 [Cp 2 U(-Cl)]3 + H2 (26)
3
(9)
A cationic bis(pentamethylcyclopentadienyl)uranium(III)
complex has been reported. [Cp 2 U(THF)2 ][BPh4 ] is gener-
One of the most remarkable reactions of Cp 3 U is that ated by protonation of the complex Cp 2 U[N(SiMe3 )2 ] with
with dinitrogen at moderate pressure (80 psi) to yield the [NH4 ][BPh4 ].67
8 ACTINIDES: ORGANOMETALLIC CHEMISTRY
2.7 CpAnX2 Complexes distances are to the three nonbridging carbons in a tri-hapto or
3 fashion (ThCave = 2.83 A).70
Mono-ring cyclopentadienyl complexes of trivalent The indenide anion is analogous to the cyclopentadienide
actinides are exceedingly rare. The borohydride ligated anions anion, but differs significantly in electronic structure and steric
CpU(BH4 )3 and Cp*U(BH4 )3 have been reported through requirements. Tris(indenyl)thorium(IV) and uranium(IV)
sodium amalgam reduction of the corresponding uranium(IV) halides, (C9 H7 )3 AnX, have been prepared by metathesis of the
precursors.68 Neutral Cp*UI2 (THF)3 is readily prepared by halide ligands of AnX4 with 3 equivalents of indenyl potassium
treatment of UI3 (THF)4 with one equivalent of KCp* in THF in THF solution.71 Mono(indenyl)thorium, -uranium, and
solution. The solid-state structure reveals a pseudo-octahedral -neptunium compounds of the type (C9 H7 )AnX3 L, where
coordination geometry with a trans mer arrangement of L is a Lewis base, can be prepared by modifying the reaction
iodide and THF ligands, as indicated in (10).59 stoichiometry.
The molecular structure of (C9 H7 )3 UCl is indicated in
(12) and reveals a distorted tetrahedral coordination geometry
with 5 -indenyl ligation. The UCl distance is 2.593(3) A,
and the average UCring distance is 2.78 A, with a range
I THF of 2.67(1) 2.89(1) A. The (C9 H7 )3 ThX compounds can be
U converted to alkoxide and tetrahydroborate derivatives by
THF straightforward metathesis.72 In the case of (C9 H7 )3 UCl plus
I
NaBH4 , reduction to trivalent (C9 H7 )3 U(THF) is reported
THF to occur. Complexes similar to (5 -C9 H7 )3 MCl compounds
(10) have also been prepared and characterized with substituted
indenyl ligands.
In the presence of excess pyridine, this complex can be
converted to the analogous pyridine adduct Cp*UI2 (py)3 . X
Cp*UI2 (THF)3 will react further with KCp* to generate
the bis-ring product, Cp 2 UI(THF), or will react with two
equivalents of K[N(SiMe3 )2 ] to produce Cp*U[N(SiMe3 )2 ]2 . U
The solid-state structure of the bis(trimethylsilyl)amide
derivative reveals close contacts between the uranium center
and two of the methyl carbons (2.80(2), 2.86(2) A).64
O
O O
Th
K THF THF
Cl Cl
(16)
U
ThO distance is 2.57(2) A, and the average ThCring distance
is 2.72(2) A.91
The aforementioned preparative routes are not applicable
to mono-cot uranium(IV) complexes. The groups of Cloke,92
Streitwieser,93 and Ephritikhine94,95 have developed several
(15)
successful routes for the preparation of such complexes;
some of these are indicated in equations (31 34). The
to generate the trivalent actinocenes, [K(DME)2 ]{[1,4-(t- displacement of a -coordinated ligand under oxidizing
BuMe2 Si)2 C8 H6 ]2 An} (An = Th, U).86 The complexes also conditions (equation 32) is quite remarkable and otherwise
display asymmetric AnCring distances, owing to the cap- unprecedented in organoactinide chemistry.
ping of one ring by the potassium counterion. The Th(III)
compound has a 6d1 ground state as shown by the room PhCH3
temperature EPR (see Electron Paramagnetic Resonance) U(C8 H8 )2 + U(BH4 )4 2U(C8 H8 )(BH4 )2 (31)
spectrum (gave = 1.918). THF
U(C8 H8 )2 + I2 U(C8 H8 )I2 (THF)2 + C8 H8 (32)
Intermolecular electron-transfer rates have been studied for
THF
uranocene and substituted derivatives of uranium, neptunium, (Et2 N)2 UCl2 + K2 C8 H8 (C8 H8 )U(NEt2 )2 (THF) + 2KCl
and plutonium by examining the variable-temperature NMR (33)
spectra of mixtures of (C8 H8 )2 An and [(C8 H8 )2 An] .87 In all
OEt2
cases, electron-transfer rates are rapid. Specific rates could not U(C8 H8 )2 + 3LiNEt2 Li[(C8 H8 )U(NEt2 )3 ] + Li2 C8 H8 (34)
be derived for uranium and plutonium derivatives owing to the
small chemical shift differences between analogous An(IV)
The mono-cot complexes are more reactive than their
and An(III) compounds, but in the case of (t-BuC8 H7 )2 Np,
actinocene congeners, and all react with Lewis bases to
the rate has been estimated to be of the same order
form adducts, such as (C8 H8 )UCl2 (PMe3 ), (C8 H8 )UCl2 (py)2 ,
of magnitude as comparable lanthanide cyclooctatetraene
(C8 H8 )UI2 (HMPA)2 , and (C8 H8 )U(BH4 )2 (THF). In addition,
compounds (107 M1 s1 ).87
considerable effort has been expended on the metathesis of the
halide ligands to produce mono(cyclooctatetraenyl) actinide
3.2 (cot)AnX2 Complexes amides and alkyls (equations 35 and 36).90,95
THF
Li[(C8 H8 )U(NEt2 )3 ] + TlBPh4
(C8 H8 )U(NEt2 )3 + Tl0 + LiBPh4 (37)
U O
THF
(C8 H8 )U(NEt2 )2 (THF) + AgBPh4
[(C8 H8 )U(NEt2 )2 (THF)][BPh4 ] + Ag0 (38)
THF
OR
Cp UI2 (THF)3 + K2 C8 H8
R
Cp U(C8 H8 )(THF) + 2KI (41) O U
PhCH3
2(C8 H8 )UCp (THF) + C8 H8 [(C8 H8 )Cp U]2 (-C8 H8 ) Quite recently, Hanusa and coworkers have isolated
(42) the bulky allyl complexes [(Me3 Si)n C3 H5 n ]4 Th (n = 1,2)
12 ACTINIDES: ORGANOMETALLIC CHEMISTRY
from the reaction of ThBr4 (THF)4 and four equivalents and those of (C6 H6 )U(AlCl4 )3 and [(C6 Me6 )2 U2 Cl7 ][AlCl4 ]
of K[(Me3 Si)n C3 H5 n ] in THF at 78 C. The isolated are shown schematically in (19) and (20). The arene ligands
complexes are stable up to 90 C (n = 1) or 124 C (n = 2) are all bonded in an 6 fashion with relatively long average
and are the first structurally authenticated homoleptic (see UCring distances in the range of 2.92 2.94 A.110
Homoleptic Compound) Th-allyl complexes. The ThC
distances in [(Me3 Si)2 C3 H3 ]4 Th range from 2.617(5) to C6 H6
2.892(5) A, a spread (0.275 A) similar to that of the ThC UCl4 + Al + AlCl3 (C6 H6 )U(AlCl4 )3 (48)
bond lengths in the slipped indenyl complex (C9 H7 )4 Th C6 Me6
UCl4 + Zn + xs AlCl3 [(C6 Me6 )2 U2 Cl7 ][AlCl4 ] (49)
(2.66(3) 2.97(4) A).105
THF
UCl3 (THF)x + 3K(2,4-Me2 C5 H5 )
(2,4-Me2 C5 H5 )3 U + 3KCl (46)
Cl Cl
Cl
Cl Cl
potassium borohydride in the presence of the crown ether.107 U U
The reaction of (2,4-Me2 C5 H5 )3 U with [Et3 NH][BPh4 ] gener- Cl
ates the cationic U(III) complex [(2,4-Me2 C5 H5 )2 U][BPh4 ].107
The tetravalent uranium derivatives (2,4-Me2 C5 H5 )2 U(BH4 )2 Cl
and (2,4-Me2 C5 H5 )U(BH4 )3 have been synthesized by the
reactions of (2,4-Me2 C5 H5 )3 U with TlBH4 , or U(BH4 )4 with
K(2,4-Me2 C5 H5 ), respectively.108 (20)
Similar reactions have also been carried out with the related
6,6-dimethylcyclohexadienyl ligand. Reaction of U(BH4 )4
Ephritikhine showed that thermal reduction of U(BH4 )4
with K(6,6-Me2 C6 H5 ) provides the bis(ligand) compound,
in mesitylene produces (C6 H3 Me3 )U(BH4 )3 .111 Unlike the
(5 -6,6-Me2 C6 H5 )2 U(BH4 )2 as shown in equation (47).108
tetrachloroaluminate complexes, this complex is soluble in
THF
toluene and NMR spectroscopy shows that the arene ligand
U(BH4 )4 + 2K(6,6-Me2 C6 H5 ) undergoes reversible dissociation. X-ray diffraction reveals
(BH4 )2 U(5 -6,6-Me2 C6 H5 )2 (47) a pseudotetrahedral coordination geometry with an average
UC distance of 2.93 A.
More recently, Cummins and coworkers have reported
that reduction of tetravalent uranium amide complexes pro-
vides an interesting series of bridging (see Bridging Ligand)
5 ARENE (See Arene Complexes) COMPLEXES
arene complexes. Reduction of [N(t-Bu)Ar]3 UI (Ar = 3,5-
Me2 C6 H3 ) by KC8 in toluene generates the complex [N(t-
The first organoactinide arene complex (6 - Bu)Ar]2 U(-6 ,6 -C7 H8 )U[N(t-Bu)Ar]2 . Structural charac-
C6 H6 )U(AlCl4 )3 was prepared in 1971 by Cesari and terization reveals that the complex contains a bridging toluene
coworkers via the Friedel Crafts reduction of UCl4 in benzene molecule bound symmetrically to the two metal centers
(equation 48).109 This reducing Friedel Crafts methodology (21).112
was developed further by Cotton et al., who isolated a series The UCring distances are short relative to other 6 -arene
of hexamethylbenzene complexes whose stoichiometry was complexes, ranging from 2.503(9) to 2.660(8) A. In addition,
dependent upon the reaction conditions and the quantities of there is a slight distortion in the bound toluene ligand; the
AlCl3 and reducing agent (Zn or Al) used in the synthesis. One average CC distance increases by approximately 0.04 A
of these reactions is shown in equation (49). The molecular compared to that found in free toluene. Density functional
structures of all of these complexes have been determined, calculations carried out on the molecule suggest that four
ACTINIDES: ORGANOMETALLIC CHEMISTRY 13
R U
N
N R
U U
N R
N
R
(22)
Homoleptic tetrabenzyl complexes are prepared by reaction prepared from the corresponding chlorides via the routes
between ThCl4 and benzyllithium in THF solution at shown in equations (56) and (57).130 Thermolysis of
low temperature (equation 53).126 It is unlikely that these the methyl compounds (equation 57) or treatment of
complexes are 1 -alkyls, since the X-ray structure of ClAn[N(SiMe3 )2 ]3 with alkylating agents other than those
Cp*Th(CH2 Ph)3 revealed multihapto coordination of the shown in equations (56) and (57) leads to -hydrogen atom
benzyl ligand.127 abstraction and formation of the corresponding metallacycles
(see Metallacycle) (equation 58).131 The metallacycles exhibit
THF a rich chemistry themselves, some of which is outlined in
ThCl4 + 4LiCH2 Ph Th(CH2 Ph)4 + 4LiCl (53)
20 C Scheme 2.
Me3Si SiMe3
U SiMe3
7.3.1 Tris(cyclopentadienyl) Alkyls
CH
CH
As noted earlier, the chloride ligand in Cp3 AnCl (An = Th,
CH
U, Np) is labile and this feature has facilitated the synthesis
SiMe3 of a great many tris(cyclopentadienyl)actinide(IV) alkyl
Me3Si
SiMe3
derivatives by metathesis with alkyllithium or Grignard
reagents. The properties and reactivity of these complexes
(26) have been extensively studied and reviewed.4 They exhibit
remarkable thermal stability. As members of the general
class of Cp3 AnX complexes, they adopt the ubiquitous
7.2 Phosphine and Amido Stabilized Alkyls
pseudotetrahedral coordination geometry that was illustrated
Andersen has found that chelating phosphine ligands earlier in (2).
greatly enhance the thermal stability of certain actinide The Cp3 ThR complexes have been used to measure
alkyls. Methyl, benzyl, and mixed methyl/benzyl derivatives metal alkyl bond disruption enthalpies for a series of thorium
can be prepared according to equation (55) using dmpe.129 alkyl complexes for both solution and gas phases. The
Equation (55) does not provide stable compounds with alkyl thorium carbon bonds appear to be relatively strong when
groups containing -hydrogen atoms. compared to other metal carbon linkages, and solution bond
disruption enthalpies range from ca. 75 to 90 kcal mol1 .15
Et2 O The reactivity of Cp3 AnR complexes has been studied
AnCl4 (dmpe)2 + 4LiR AnR4 (dmpe)2 + 4LiCl (55) in some detail and is dominated by insertion of CO, CO2 ,
and CNR ligands to give 2 -acyl, 2 -carboxylate, and 2 -
Thermally stable thorium(IV) and uranium(IV) methyl iminoalkyl complexes. The resulting insertion products are
compounds of the type MeAn[N(SiMe3 )2 ]3 have been illustrated schematically in (27), (28), and (29), respectively.
16 ACTINIDES: ORGANOMETALLIC CHEMISTRY
R
N C
(Me3Si)2N
An
(Me3Si)2N NEt2
O CH2 N SiMe2
C
(Me3Si)2N (Me3Si)2N
An Me3Si An
(Me3Si)2N SiMe2 (Me3Si)2N
N N(SiMe3)2
SiMe3
RCN HNEt2
CO
R
R
H2 O O C
OR C
(Me3Si)2N ROH (Me3Si)2N R R (Me3Si)2N
An An SiMe2 An
(Me3Si)2N (Me3Si)2N (Me3Si)2N
N(SiMe3)2 N N SiMe2
SiMe3 Me3Si
ButNC ArSH
N
But
SAr
N CH2
C (Me3Si)2N
(Me3Si)2N An
An
(Me3Si)2N (Me3Si)2N
(Me3Si)2N SiMe2 An N(SiMe3)2
N N
(Me3Si)2N
SiMe3
Scheme 2 Some reactions of the actinide (IV) metallacycles of the type [(Me3Si)2N]2An SiMe2
N
SiMe3
Cp* CH3
Th
Cp*
But
Cp* OR Cp*
Th CH4 Th Si
Cp* Si(CH4)4 Cp*
But
CMe4
ROH
Cp*
Th
Cp*
H2 P(CH3)3
Cp* H CMe4 CMe4 Cp*
Th Th P
Cp* Cp*
H
Cp*
Th
Cp*
these compounds relative to those compounds prepared with anticipated Cp 2 U(H)Cl but rather a trinuclear uranium(III)
simple alkyls such as methyl and neopentyl. In contrast to the chloride compound [Cp 2 U(-Cl)]3 mentioned earlier.66
literature on Cp 2 AnR2 compounds, very little is known about
the chemistry of Cp*AnR3 compounds. C5 H12
Cp 2 UH2 + dmpe Cp 2 U(dmpe)H + 0.5H2 (65)
Et2 O
Cp AnCl3 (THF)2 + 3LiR Cp AnR3 + 3LiCl (63)
One (C5 H5 )3 UX molecule that has proven elusive
is Cp3 UH. As noted above, uranium(IV) hydrides can
decompose via intermolecular reactions that produce hydrogen
and generate uranium(III) products. Surprisingly then, the
8 HYDRIDE COMPLEXES complexes [5 -RC5 H4 ]3 UCl (R = SiMe3 , CMe3 ) react with
KBEt3 H in THF to yield the thermally stable hydrides
[RC5 H4 ]3 UH.139 Related thorium compounds, [RC5 H4 ]3 ThH
8.1 Peralkylcyclopentadienyl Hydrides
and Cp 3 ThH, can also be prepared.140,141
The first organoactinide hydrides (see Hydride Complexes Actinide hydrides are rather hydridic and undergo rapid
of the Transition Metals) were prepared by hydrogenolysis reactions typical of such systems; for example, reactions
of the bis(pentamethylcyclopentadienyl)alkyls, Cp 2 AnR2 with ketones and halocarbons provide actinide alkoxides and
(equation 64).33 These reactions are thought to take place halides, respectively. Rapid quantitative addition of terminal
via -bond metathesis, as depicted in Scheme 4. The neutron alkenes (the reverse of -hydride elimination) is consistent
diffraction structure of [Cp 2 ThH2 ]2 has been determined: with the known bond disruption enthalpies (equation 66).15
it adopts the geometry indicated in (31).137 The mean
ThH(terminal) and ThH(bridge) distances are 2.03(1) and An H + An
(66)
2.29(3) A, respectively. The HThH angle is 58(1) and
the ThHTh angle is 122(4) . These angles and the ThTh
separation of 4.007(8) A indicate minimal direct metal metal
interaction.
9 CARBONYL COMPLEXES
C5 H12
Cp 2 AnR2 + H2 Cp 2 AnH2 + 2RH
(64)
Stable homoleptic (see Homoleptic Compound) mononu-
clear and polynuclear complexes (see Polynuclear Organo-
metallic Cluster Complexes) of carbon monoxide are known
for most of the transition elements (see Carbonyl Complexes
of the Transition Metals). One might ask whether an actinide
H
H
carbonyl compound, such as U(CO)6 , an analog of the well-
Th Th known group 6 carbonyls M(CO)6 (M = Cr, Mo, W), could
H also be prepared. Uranium carbonyls, U(CO)x , have in fact
H been observed in cryogenic matrices. The cocondensation of
uranium vapor with CO in an argon matrix at 4 K yields
species clearly identifiable as uranium carbonyls U(CO)x by
(31) IR spectroscopy.142 Derived force constants suggest bonding
patterns similar to those observed for zerovalent early transi-
tion and lanthanide metal carbonyls. Complete decomposition
[Cp 2 UH2 ]2 is unstable with respect to the uranium(III) of these uranium carbonyls occurs at temperatures above ca.
hydride [Cp 2 UH]x , which can be trapped with dmpe 30 K. In dilute matrices, the chemistry of uranium atoms and
(equation 65).138 Earlier, Marks and coworkers had observed CO is much more complex and initially leads to insertion of
that the reaction of Cp 2 U(R)Cl with H2 does not provide the uranium into the CO bond to form CUO.143
The first stable actinide complex of carbon monoxide was
prepared by reaction of (Me3 SiC5 H4 )3 U (Cp 3 U) with CO in
d d+
solution or in the solid state to produce Cp 3 U(CO), which
H H reversibly dissociates CO.144 Cp 3 U(CO) exhibits a carbonyl
XnAn R + H2 XnAn R XnAn H + R H
stretch in the IR spectrum at 1976 cm1 , or approximately
170 cm1 lower than the CO for free carbon monoxide. This is
d+ d
taken as an indication of uranium-to-carbonyl -back bonding
(see Back Bonding). Electronic structure calculations on the
Scheme 4 Sigma bond metathesis of actinide-alkyl bonds model complex Cp3 UCO indicated a significant U 5fCO 2
ACTINIDES: ORGANOMETALLIC CHEMISTRY 19
back bonding, which results in a stabilization of the uranium 5f distances yet measured (2.29 A) and large UCP angles
atomic orbitals.145 Other (Rn C5 H5 n )3 U(CO) complexes have (143 ), indicative of uranium carbon multiple bond
been prepared and characterized.144 The molecular structure character.149 The negative charge on the -carbon in these
of (C5 Me4 H)3 U(CO) (CO = 1880 cm1 ) possesses a short systems is stabilized by the presence of an electron-
UCCO bond distance of 2.383(6) A.146 Comparison of the withdrawing heteroatom substituent. Reactions of these
CO stretching frequencies for a series of compounds with compounds with weak acids and polar unsaturated molecules
different ring substituents indicates that electron-donating are summarized in Scheme 5. Despite repeated efforts, no
substituents increase the electron density at the metal center one has yet developed the requisite synthetic methodology
and increase metal-to-ligand back donation.146 Cp 3 U(CO) to prepare actinide alkylidenes (see Alkylidene), Ln An=CR2 .
is a more recent addition to the family of tris-Cp uranium The authors are, however, optimistic that the synthesis of such
carbonyl complexes.147 The UCCO distance in the latter molecules will be achieved in the next few years.
complex is 2.485(9) A and its CO stretching mode is located
at 1922 cm1 .
Gilje, Cramer, and their coworkers have studied the syn- Studies of organoactinide surface chemistry and catalysis
thesis, structure, and reactivity of uranium(IV) phosphoylide have been carried out by the Marks group under rigorously
complexes prepared according to equation (67).148 The X-ray anhydrous/anaerobic conditions on either partially dehy-
droxylated alumina (PDA) or DA at surface coverages of
THF 0.25 0.50 molecules nm1 .150 The PDA and DA surfaces
Cp3 UCl + Li(CH2 )2 PRR Cp3 UCHPMeRR + LiCl
are represented schematically in equation (68). Product yields,
(R, R = Me, Ph) (67) isotopic labeling, and surface reactivity indicate that the irre-
versible -alumina adsorption chemistry of Cp 2 AnMe2 can
structure of Cp3 UCHPMe2 Ph and the neutron diffraction be described by three methane-evolving pathways (equa-
structure of Cp3 UCHPMe3 revealed the shortest UC tions 69 71). Equation (69) dominates on PDA. On DA,
Cp Ph
N PPh2Me
Cp
U C C
Cy Cp O H
Cp N
Cp Cp
U C Cp
C PPh2Me U C CPh
Cp PhNCO Cp
H
CyNC Cp HC2Ph
Cp PPh2Me
U C
Cp H
HNPh2 CO
Cp Cp O
MeCN
Cp Cp
U NPh2 U C
Cp Cp C PPh2Me
H
Cp H
C PPh2Me
Cp
U N C
Cp Me
950 C H2O
Scheme 6 Proposed catalytic cycle for alkene hydrogenation
mediated by supported cationic complexes derived from Cp 2 ThMe2
O O
Al O Al O Al
DA
(68)
for propylene hydrogenation greater than the active sites of
Pt/SiO2 under the same conditions (Nt 2 s1 vs. 0.05 s1
Me
at 63 C). Kinetic/mechanistic studies are in accord with
CH4 Cp*2An
Cp*2AnMe2 O (69) the sequence outlined in Scheme 6 but leave unanswered
Al
atomic-level questions regarding the exact nature of the
organoactinide surface interaction. This question can, how-
CH4 ever, be addressed using 13 C cross polarization with magic
Cp*2AnMe2 Cp*2An Al (70)
O angle spinning (CPMAS) NMR spectroscopy. The spectra of
CH4
Cp 2 ThMe2 /DA have been completely assigned and lead to
Cp 2 AnMe2 Cp (5 , 1 -C5 Me4 CH2 )AnMe (71) the remarkable conclusion that a methide ion is transferred
from the actinide center to a Lewis acid site on the surface.
Complexes such as Cp 2 ThMe2 are only marginally active This is shown pictorially in (32). The CPMAS spectra of
for alkene hydrogenation or polymerization in homogeneous Cp 2 ThMe2 on PDA is quite different and indicates structure
solution (see Oligomerization & Polymerization by Homo- (33).151
geneous Catalysis). Adsorption on DA effects a dramatic The tetraallyl complex Th(3 -C3 H5 )4 supported on
enhancement in catalytic activity. Using propylene hydro- dehydroxylated -alumina is an outstanding heterogeneous
genation as a probe reaction, kinetic experiments revealed catalyst for arene hydrogenation that rivals the most active
catalytic activities comparable to those of heterogeneous platinum metal catalysts in activity. Th(3 -C3 H5 )4 /DA also
platinum metal catalysts. Separate poisoning studies indi- catalyzes the rapid and selective deuteration of linear and
cated that only 4% of the actinide sites sustain the bulk of cyclic alkanes. CH reactivities fall in the order primary >
hydrogenation activity. These sites have turnover frequencies secondary > tertiary.152
+
CH3 surface CH3
An An
CH3 _
CH3
(32)
ACTINIDES: ORGANOMETALLIC CHEMISTRY 21
p
(ff ) e3u
e3g
p
dp
dd dp dd
6d ds
fd
fp
5f fs
ff p
(fd) e2u
(dd) e2g
p
(fp) e1u
(dp) e1g
p
fd fp a2u
a1g
a stronger metal ligand d orbital interaction. Computational Although only one valence electron resides in a 5f-localized
studies have been reported for a fair number of complexes orbital on uranium in [U(C7 H7 )2 ] , a formal oxidation state of
containing cyclopentadienyl ligands. Collectively, all the +3 (5f 3 ) was assigned, based on the fact that the HOMO 3e2
calculations on complexes containing cot and Cp ligands molecular orbitals (occupied by four electrons) are nearly 50%
indicate that the 6d atomic orbitals of the early actinides 5f in character, and so two of these electrons were assigned
dominate the metal ligand bonding and that the 5f orbitals to the metal. EPR and electron-nuclear double resonance
are relatively unaffected, and serve as a reservoir for the (ENDOR) studies of [(C7 H7 )2 U] suggest that the complex
valence electrons. Relativistic corrections tend to increase could be treated as 5f1 , with a ground-state molecular orbital
the contribution of the uranium 6d orbitals and decrease comprised of both 5f and 5f orbitals.114
the contribution of the 5f orbitals. This view of bonding The role of actinide virtual 6d orbitals and relativistic
has been extended to heterobimetallic complexes (see Dinu- corrections in describing metal ligand bonding has been
clear Organometallic Cluster Complexes), which contain a extended to sophisticated calculations on trivalent alkyl
direct actinide transition metal interaction such as Cp 2 Th(- complexes AnMe3 (An = U, Np, Pu)159 and pentavalent
PPh2 )2 Pt(PMe3 ) and (I)Cp 2 ThRuCp(CO)2 . Calculations on uranium imido complexes (R2 N)3 U=NR.160 The calculations
these systems indicate a metal metal bonding HOMO made on AnMe3 (An = U, Np, Pu) were carried out at the complete
up of an occupied transition metal d orbital donating into a active space (CAS)-SCF level including relativistic core
vacant actinide 6d acceptor orbital, and is best described as a potentials, and indicate that the experimentally determined
dative metal metal bond.20,40,157 pyramidal geometry is more stable than a planar geometry in
A density functional theoretical study has examined the AnL3 complexes owing to involvement of 6d character in the
question of bonding in the complexes [(7 -C7 H7 )2 An]n AnC bonding orbitals upon bending. The relativistic discrete
(Th, Pa, U, Np, Pu, Am).158 It was found that the 5f - variational-local density functional (DV-LDF) calculations
symmetry orbitals not only participate in the bonding with on (NR2 )3 U=NR complexes also point to the importance of
e2 p orbitals of the C7 H7 rings, but are as important 6d orbital participation and indicate the presence of U=NR
as the symmetry appropriate 6d orbitals in stabilizing the multiple bonding. These calculations have been used to
ligand-based fragment orbitals. The 5f percentage in frontier reassign the gas-phase PES of [(Me3 Si)2 N]3 U=N(SiMe3 ).161
e2 molecular orbitals increases across the series, and the Electronic structure calculations, including relativistic core
contribution of the 6d orbitals gradually decreases across the potentials and the spin-orbit coupling, have been carried out
series. The ground electron configurations, ionization energies, on the C28 , Pa@C28 , and U@C28 species.162 The ground state
electron affinities, and AnC7 H7 bond energies are strongly of C28 is described well by Hartree-Fock (see Hartree Fock
affected by these effects. Theory) wave functions, and the computed electron affinity
ACTINIDES: ORGANOMETALLIC CHEMISTRY 23
and ionization potential are similar to those of C60 . Strong 5. T. J. Marks and A. Streitwieser Jr, in The Chemistry of
metal-cage binding is found for Pa@C28 and U@C28 , similar the Actinide Elements, eds. J. J. Katz, G. T. Seaborg, and
to that in U(C8 H8 )2 . The ground electronic states depend on L. R. Morss, Chapman & Hall, New York, 1986, Chap. 22.
the order of the lowest energy cage and metal 5f orbitals, 6. J. Takats, in Fundamental and Technological Aspects of
with ( )1 and ( )1 (5f )1 found to be the ground electronic Organo-f-Element Chemistry, eds. T. J. Marks and I. Fragala,
configurations for the Pa and U complexes, respectively. The Reidel, Dordrecht, 1985, p. 159.
uranium fullerene is calculated to be diamagnetic. 7. I. Santos, A. Pires de Matos, and A. G. Maddock, Adv.
Organomet. Chem., 1989, 34, 65.
8. B. E. Bursten and R. J. Strittmatter, Angew. Chem., Int.
Ed. Engl., 1991, 30, 1069; C. J. Burns and B. E. Bursten,
13 RELATED ARTICLES Comments Inorg. Chem., 1989, 9, 61.
9. M. Ephritikhine, Chem. Rev., 1997, 97, 2193; M. Ephritikhine,
New J. Chem., 1992, 16, 451.
Bonding Energetics of Organometallic Compounds; Car-
10. N. Kaltsoyannis, Chem. Soc. Rev., 2003, 32, 9.
bon: Fullerenes; Carbonyl Complexes of the Transition
Metals; Dinuclear Organometallic Cluster Complexes; Het- 11. Uranium metal is available from Oak Ridge National
erogeneous Catalysis by Metals; Hydride Complexes of Laboratory. The Oak Ridge isotope catalog is available on
the Transition Metals; Hydrogenation & Isomerization of line at www.ornl.gov/isotopes/catalog.html.
Alkenes; Mechanisms of Reaction of Organometallic Com- 12. E. O. Fischer and A. Treiber, Z. Naturforsch., 1962, 173,
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K. Panchanatheswaran, and J. W. Gilje, J. Am. Chem. Soc., Acknowledgment
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and J. W. Gilje, Organometallics, 1987, 6, 41; R. E. Cramer, The authors are grateful to the Division of Chemical
J. W. Jeong, and J. W. Gilje, Organometallics, 1987, 6, 2010; Sciences, Geosciences, and Biosciences, Office of Basic
R. E. Cramer, M. A. Bruck, F. Edelman, D. Afzal, J. W. Gilje, Energy Sciences, U.S. Department of Energy, for their support
and H. Schmidbauer, Chem. Ber., 1988, 121, 417. of actinide organometallic chemistry research at Los Alamos
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358.
Alkali Metals: Inorganic greases, of toughened glass, and in porcelain and ceramics
production. Organolithium reagents (e.g. n-butyllithium) are
Chemistry of increasing importance as reagents in synthetic organic
chemistry6 (see Alkali Metals: Organometallic Chemistry)
and as anionic polymerization initiators to produce, for
Wing-Por Leung & Queenie Wai-Yan Ip example, styrene butadiene copolymers for car tyres (see
The Chinese University of Hong Kong, Hong Kong, China Oligomerization & Polymerization by Homogeneous Cataly-
sis).7 Sodium chloride is of particular importance, being more
Based in part on the article Alkali Metals: Inorganic Chemistry by used for inorganic chemical manufacture than any other mate-
Francis S. Mair & Ronald Snaith which appeared in the Encyclopedia rial. In the future, lithium (especially) and sodium are likely
of Inorganic Chemistry, First Edition. to assume even more commercial importance: lithium metal
as a source of tritium (from the 7 Li + neutron reaction) for
1 Introduction 1 nuclear fusion processes and as a nuclear reactor coolant, and
2 The Elements 1 both elements as likely components of energy storage systems
3 Compounds 6 for off-peak electricity and of batteries for electric cars.8
4 Coordination Compounds 14
5 Metal-organics 18
6 Related Articles 20
7 References 20 2 THE ELEMENTS
the ore is heated with CaO to give LiOH which is then plant fertilizers. Other less employed, but still important,
converted to the chloride. Fused low-melting eutectics such as potassium compounds include the hydroxide, used mainly to
LiCl + KCl (450 C) and NaCl + CaCl2 (505 C) are used in produce phosphates for liquid detergents; the carbonate, used
the electrolysis process, which employs a carbon anode and a in fluorescent lamps and in optical lenses; the bromide, which
steel cathode. The other three metals are also extracted from is the normal source of bromine gas for organic syntheses; and
their chlorides; small quantities of RbCl and CsCl are obtained the superoxide (KO2 ), which is used in breathing masks in
as by-products of lithium mineral processing. In their cases, mines and space vehicles since it reacts with traces of moisture
however, the molten metal chlorides are treated with the vapor in the breath to generate oxygen.
of a reactive metal (Na vapor at 850 C or Ca vapor at 750 C) A more unusual use of the alkali metals and their
in a countercurrent fractionating tower. compounds, but one of high industrial importance, is as
promoters of various catalysts.14 For example, addition of Li+ ,
Na+ , or K+ to MgO or CaO catalysts for the oxidative coupling
2.2 Uses of the Metals and Their Compounds of CH4 to give valuable C2 products (ethane, ethylene)
Although Rb and Cs, and their compounds, are so far improves the yields greatly; spectroscopic investigations have
mainly of academic interest, Li, Na (especially), and K, implied that [M+ O ] active sites are produced on the catalyst
and their compounds, have considerable commercial value. surface and that these sites abstract H from CH4 to give
CH 1517
Lithium metal itself 1 is used in the manufacture of alloys 3 radicals, which then couple. Similarly, catalysts
with magnesium and aluminum; these combine toughness for various transformations of syngas (H2 /CO mixtures) can
with low density and so are employed in the construction of be promoted by alkali metals, for example, doping of a
armor plate and aircraft/aerospace components (see Alloys). Cu/ZnO catalyst with Cs doubles methanol yields from H2 /CO
Until recently, the major use of sodium was also in alloy mixtures, an effect attributed partly to formation of surface
manufacture, specifically of the Pb/Na alloy needed for formate (CsCHO)18,19 (see Oxide Catalysts in Solid-state
the production of tetraethyllead, the antiknock additive (see Chemistry and see Synthesis Gas).
Lead: Organometallic Chemistry). However, the market Sodium and potassium are among the 25 or so elements
here is declining on account of the environmental problems now thought to be essential for animal life.4,20 They perform
caused by lead emissions. Molten Na (and, to a lesser but electrophysiological functions based on the fact that the
increasing extent, molten Li) is employed also as a heat- Na+ :K+ concentration ratio is different in the fluids inside
exchange coolant around nuclear reactors; properties such and outside cells. Because of these concentration gradients
as a low-melting point and low viscosity but a high heat across cell membranes, a potential difference is set up and this
capacity are valuable in this respect, although there are many is responsible for the transmission of nerve impulses. Lithium
technical problems such as melt containment, corrosion, also is of biochemical importance, but as a drug in the treatment
and reactions with the atmosphere and with the reactor of manic-depressive psychosis; in the United Kingdom, for
walls.11 example, about 1 in every 1500 people take prescribed gram
The major bulk-produced lithium salts are the stearate, quantities of Li2 CO3 daily. The inorganic pharmacology of
used to thicken and gel oils to provide lubricating greases; the lithium has been reviewed recently5,21 but it seems likely
carbonate, used as a flux in porcelain and enamel production, that its prime role is to affect the mobilization of calcium
as an additive to bauxite in aluminum production (where it into and out of cells by inhibiting certain enzymes in inositol
lowers the fusion temperature of the electrolyte and raises phosphate pathways (see Metal-based Drugs; Metal-based
the melt conductivity), and as a source of Li+ ions to Imaging Agents).
replace larger Na+ ions in the production of toughened A future bulk use of lithium and sodium might well be as
glass; and the hydroxide, which is used to absorb carbon components of batteries, particularly for off-peak electricity
dioxide from enclosed spaces such as submarines. More storage and in electric cars. The latter use will be prompted by
specialty lithium compounds find use in organic syntheses; legislation; for example, in California alone, by the year 2003,
for example, lithium aluminum hydride as a reducing 10% of all new cars (over 200 000) must be emission-free.8
agent and various organolithium compounds (particularly However, development of such batteries will be a major
n-butyllithium) as selective proton abstractor reagents and challenge. Those produced to date give limited range (having
as anionic polymerization initiators.1,6,7,12,13 Most industrial- to be recharged frequently) and poor acceleration, and they
scale compounds are derived from sodium chloride, annual are expensive, requiring complicated installation engineering.
world consumption of which is of the order of 170 million For example, sodium/sulfur batteries use a liquid sodium
tonnes. Salt itself has major uses in road clearance and anode, a sulfur cathode, and a solid electrolyte of -alumina
in animal feeds, but most of it is converted by large- (Al2 O3 ), but the snag is that they operate at 300 C.22 Similarly,
scale processes to products such as sodium hydroxide, Li/FeSx batteries employ Li and FeSx electrodes with a
chlorine, and sodium carbonate (which, taken together, molten electrolyte of LiCl/KCl at 400 C.23,24 Clearly, it would
constitute the chloralkali industry). The major potassium be preferable to avoid molten/liquid systems which require
salt is also the chloride, used to formulate most potassic elevated temperatures and which pose severe containment
ALKALI METALS: INORGANIC CHEMISTRY 3
problems. However, development of solid-only cells has been extremely long half-lives. Lithium occurs naturally as 6 Li
hampered by the scarcity of low-temperature solid electrolytes (7% abundance) and 7 Li (93%); its other three isotopes are
with good ion conductivity (see Ionic Conductors). Materials radioactive, with very short half-lives. At least one isotope of
of promise in this regard include solid LiAlCl4 (with Lix TiS2 each element has a nuclear spin (I ) and hence, potentially,
and Lix CoO2 intercalated electrodes),25 solid solutions based useful information can be gleaned from NMR studies: 6 Li,
on lithium titanium phosphate,26 and LiI4MeOH which I = 1; 7 Li, I = 3/2; 23 Na, I = 3/2; 39 K (93%), I = 3/2;
has the highest conductivity so far observed for Li+ (due 87
Rb (28%), I = 3/2; 133 Cs, I = 7/2. In practice, 7 Li NMR
to mobile complexed cations in the solid-state structure, spectroscopy has found most use; for example, in elucidating
Li(MeOH)4 + I ).27 solution structures and solution equilibria for many lithium
compounds and in monitoring concentrations and mobilities
of lithium ions in vivo.2832
2.3 Atomic, Physical, and Chemical Properties
The radii of the metals increase progressively with
Fundamental atomic and physical properties of the alkali increasing atomic number, and these elements are the largest in
metals are given in Tables 1, 2, and 3. The elements are their respective periods. Such features lead to relatively small
characterized by having electron configurations each with a first ionization energies for the atoms, and the chemistry
single s orbital electron outside a noble gas core (see Table 1). is dominated by this fact. Thus the elements are highly
Sodium and cesium are mononuclidic so that their relative reactive metals and form M+ ions in the vast majority of
atomic masses are known extremely accurately; in effect, the their compounds. The very high second ionization energies
same can be written for potassium and rubidium since their prohibit formation of M2+ species. However, although the
isotopes (of which there are three and two, respectively) have electron affinities (or electron attachment energies) are only
Ionization energies
(kJ mol1 ) Electron Electronegativity
Electronic Atomic Relative Metal affinity (Pauling
Metal configuration number atomic mass radius (A) 1st 2nd (kJ mol1 ) scale)
mildly exothermic, M ions can be produced for all the 2.4 Solutions of Alkali Metals: Solvated Electrons,
alkali metals (lithium excepted) under carefully controlled Alkalides, and Electrides
conditions (see Section 2.4).
The bonding in alkali metal compounds is held to be In common with certain other metals (e.g. the alkaline
essentially ionic, involving electrostatic attractions between earths Ca, Sr, and Ba and the lanthanides Eu and Yb) the alkali
bare or solvated M+ ions and associated anions. This reflects metals will dissolve in liquid ammonia and in certain other
the ease of formation of M+ ions and the relative weakness solvents such as organic ethers, organic amines, and HMPA
of any covalent bonds formed: the valence orbitals available (see Ammonia & N-donor Ligands). However, the solubility
to these atoms are diffuse, leading to poor overlap. This ionic is greatest in liquid ammonia and it is dramatic; for example, at
character is predictable also from the low electronegativities 50 C, 1 mole of Cs (132.9 g) will dissolve in only 2.34 mole
of the alkali metals (cf. approximate electronegativity values of NH3 (39.8 g). Discovery of this phenomenon is usually
for typical nonmetals: C 2.5, N 3.0, O 3.5, F 4.0). On this attributed to Wehl in 1863, but it now seems likely that these
basis, the degree of covalency would be highest for lithium solutions were first prepared by Davy as early as 1808. The
(Li+ is the smallest, most polarizing cation of the group). solutions have remarkable properties, particularly regarding
However, it is now generally agreed that the bonding even color, electrical conductivity, and magnetic susceptibility.
in, say, lithium carbon bonds is essentially electrostatic in Dilute solutions are blue owing to an intense absorption
nature.33,34 at a wavelength of around 1500 nm and tailing into the
Turning to the properties of the metals themselves visible. The position of this absorption, and hence the blue
(Table 2), all are soft and low-melting materials, Li to Rb color, is independent of the metal present, so indicating the
being silvery white in color and Cs golden yellow. Their presence of a species common to all such solutions. At higher
densities are extremely low (Li has the lowest density of concentrations, the color changes to a metallic bronze. The
any solid at room temperature), although they show very solutions conduct electricity and the current carrier is plainly
high electrical conductivity. Such properties reflect the fact highly mobile since the conductivity of dilute solutions is
that, with only one available valence electron per atom, considerably higher (7 or 8) than that of fully ionized salts
the metallic-binding energy is very low within rather open in water. On concentration, the conductivity first decreases
body-centered cubic lattices. Indeed, such binding energies gradually to a minimum at about 0.05 M, but then increases
decrease as the group is descended, and this is apparent in very markedly until, at around 1 M, it is comparable to that of
decreasing values for enthalpies of fusion and vaporization. the metal itself. Magnetic susceptibility measurements reveal
The vapors themselves consist of covalently bonded M2 that dilute solutions are paramagnetic to the extent of one free
diatomic molecules and, mainly, single M atoms. Within electron per metal atom. Concentration first leads to a decrease
the former, the MM bond energy is expectedly greatest when in susceptibility, and indeed solutions of minimal conductivity
M = Li, since Li has the smallest covalent radius. When are also diamagnetic; however, further concentration restores
vaporized, the elements all have characteristic flame colors: some paramagnetism.
Li crimson, Na yellow, K violet, Rb red violet, and Cs blue. The above findings have been fully reviewed.35,36 There
These arise because of the ready excitation of the single is a widespread consensus as to their interpretation and
s1 outer electron and they form the basis of the analytical it is one which tallies with the low lattice enthalpies
determination of element concentrations by atomic absorption of the alkali metals, their low ionization energies, and
spectroscopy. the high solvation energies of M+ ions. Thus, in dilute
The high reactivities of the alkali metals are reflected solutions the M atoms ionize to give M+ cations (which
in very positive electrode potentials (Table 3, shown as are solvated by NH3 molecules) and electrons (equation 1).
oxidation potentials in aqueous media). The exceptionally These electrons occupy cavities of around 3.3 A diameter
high value for lithium appears at first sight anomalous given in the liquid lattice, such cavities being produced by
that, being the smallest atom, it has the highest ionization displacement of 2 or 3 NH3 molecules which occurs because
energy. However, Li+ is the smallest of the Group 1 cations, of repulsion between each electron and the electrons within
and hence is the most heavily and most strongly solvated. these solvent molecules. This cavity concept can explain
Although only four H2 O molecules are bonded directly to why solutions are of considerably lower density than that of
each Li+ , over 20 others are affected and form a secondary liquid ammonia itself. The blue color of dilute solutions is
solvation sphere to give a total solvation number of ca. 25. due to wavefunction transitions undergone by these solvated
Hence Li+ has the most exothermic hydration energy, and (yet quasi-free) electrons. The presence of such relatively
the Li+ aq ion is the largest and the least mobile of the mobile species explains also the high conductivities and
hydrated alkali metal cations. As related in Section 4, which paramagnetism of dilute solutions. At higher concentrations,
is concerned with complexes of alkali metal compounds, solvated electrons begin to pair up and they are removed
such features are general ones and pertain to a diversity of by formation of solvated alkalide anions (equation 2).
polar solvents. Both processes lead to reductions in paramagnetism and
ALKALI METALS: INORGANIC CHEMISTRY 5
conductivity. are preparable for the heavier Group 1 metals, for exam-
ple, [Cs(18-crown-6)]+ Cs , and mixed-metal species are
also known, for example, [Rb(15-crown-5)]+ Na . Recently,
M(s)
M(NH3 )
M+ (NH3 ) + e (NH3 ) (1)
(dispersed)
structures of alkalides contain mixed-sandwich complexes
of alkali metal cations with 18-crown-6, 15-crown-5, and
M(NH3 ) + e (NH3 )
M (NH3 ) (2)
12-crown-4 have been determined.43 An unusual barium aza-
cryptand sodide Ba2+ (H5 Azacryptand[2.2.2] )Na 2MeNH2
Liquid ammonia solutions of the alkali metals have found has been synthesized and structurally characterized by X-
use as strong and selective reducing agents in diverse areas ray crystallography and 23 Na MAS NMR.44 Novel dimer of
of chemistry. Such solutions are quite stable providing the (Na2 )2 has been found in the crystal lattice with internuclear
ammonia is pure and anhydrous, and especially providing distance of 4.17 A, 1.3 A shorter than the average diameter
that no transition metal ions are present. Such ions catalyze (5.5 A) of Na . Dimers of K and Rb and chains of Rb
decomposition to metal amide (equation 3). Synthetic uses in and Cs have also been observed.45 Solid-state NMR spectra
inorganic chemistry include the generation of transition metal of the homo-metallic systems reveal separate resonances for
species in unusually low-oxidation states (see Section 3.5) M+ and M , confirming that they behave as independent enti-
and of clustered polyanions of main group elements, for ties. Solution NMR spectra also give sharp signals for M ,
example, Sn9 4 , Pb7 4 , As5 3 , and Sb7 3 . A recent use with indicating that the anion is essentially unsolvated.
considerable scope has been the reduction of transition metal It is also possible to prepare crystalline electrides
salts to give small (2 15 nm diameter) metal particles.37 in which a trapped electron acts in effect as the
However, probably the most widespread application of anion. The bulk of the excess electron density in
these alkali metal solutions has been as reducing agents electrides resides in the X-ray empty cavities and
in organic synthesis6,38 since they will frequently effect in the interconnecting channels. Structures of electri-
reductions that are otherwise impossible. The reagents have dides [Li(2,1,1-crypt)]+ e [K(2,2,2-crypt)]+ e , [Rb(2,2,2-
been especially valuable in peptide synthesis.39 Among these crypt)]+ e , [Cs(18-crown-6)2 ]+ e , [Cs(15-crown-5)2 ]+ e
alkali metal reagents, sodium naphthalenide is commonly and mixed-sandwich electride [Cs(18-crown-6)(15-crown-
used as a one-electron donor in these organic reduction 5)+ e ]6 18-crown-6 are known.4648 Silica-zeolites with pore
reactions. However, two-electron transfer via two-step has diameters of 7 A have been used to prepare silica-based
been proposed in organic reactions involving K+ (18-crown-
electrides.49 The potassium species contains weakly bound
6)K .40,41
electron pairs which appear to be delocalized, whereas the
cesium species have optical and magnetic properties indica-
e NH3 + e NH3 H2 + NH2 (3)
tive of electron localization in cavities with little interaction
2M(s)
M (solv) + M (solv)
+
(4) between the electrons or between them and the cation. The
structural model of the stable cesium electride synthesized by
As mentioned above, solutions of the alkali metals (except intercalating cesium in zeolite ITQ-4 has been confirmed by
Li) contain solvated M anions as well as solvated M+ cations the atomic pair distribution function (PDF) analysis.50 The
and solvated electrons;35 indeed, there is some evidence to synthetic methods, structures, spectroscopic properties, and
suggest that the reducing abilities of such solutions are due magnetic behavior of some electrides have been reviewed.51
largely to the presence of these anions. Alkalide containing Theoretical study on structural and electronic properties of
Li has not been observed in solution or in the solid state, inorganic electrides has also been addressed recently.52
which is due to the strong solvation/complexation of Li+ .42
Isolation of stable solids containing these alkalide anions has
depended on driving the equilibrium shown in equation (4) 2.5 Metal Atoms and Clusters Trapped in Zeolites and
to the right and then on protecting the anion from the polar- Graphite
izing effects of the cation. Both aims have been realized
by using two-dimensional and three-dimensional macrocyclic The section above described how alkali metal species such
ethers (crowns and cryptands, respectively; see Section 4.3). as solvated M+ ions and M ions can be formed and isolated
The cryptands are particularly effective in encapsulating M+ within the lattices of certain liquid solvents. It is also possible
cations. For example, addition of Na metal to a solution to obtain single alkali metal atoms (M) and clusters (usually
of N[(CH2 CH2 O)2 CH2 CH2 ]3 N (called 2,2,2-crypt) in EtNH2 cationic ones, (M)n x+ ) in various solid hosts such as zeolites
allows isolation of golden yellow crystals with a metallic and graphite. There is considerable interest in clustered species
luster, [Na(2,2,2-crypt)]+ Na . In the crystal, each Na ion since they are especially relevant to the question of what has
sits over an open face where the captured Na+ is visible been called the metal/nonmetal transition, that is, how many
through the crypt molecule. The anion has an apparent radius atoms need to be gathered together before metallic (rather than
of around 2.2 A, cf. 1.02 A for six-coordinate Na+ and 1.54 A molecular, nonmetallic) properties become apparent? The few
for the covalent radius of Na. Similar crystalline alkalides electron alkali elements lend themselves to state-of-the-art
6 ALKALI METALS: INORGANIC CHEMISTRY
quantum mechanical calculations which probe this question, electrons between graphite and the metal. Interest in them
and this area has been reviewed recently.53 centers mainly on this latter property. In this context, it has
Zeolites (e.g. Zeolite A, (1)) are a class of aluminosilicates recently been found60 that fullerenes such as C60 (isolated
which are built up from corner-sharing SiO4 and A1O4 from soot extracts) can also be doped by alkali metal
tetrahedra arranged in three-dimensional networks and which vaporization to give films such as C60 K3 and C60 Rb3 which
provide channels and cavities of molecular dimensions (see have superconductivity transition temperatures of around 20 K
Zeolites). Electroneutrality is maintained by the presence of (see Carbon: Fullerenes).
metal (usually alkali metal) cations. Clustered cationic species
such as Na3 2+ , Na4 3+ , Na5 4+ , Na6 5+ , K3 2+ , and K4 3+ , as well
as neutral alkali metal particles, (M)n , can be formed within
such hosts by a variety of methods including high-vacuum
deposition of metal atoms,54 treatment of the zeolite with an
alkali metal azide (which decomposes to give the metal),55
K K K K
and reduction of the cations already present in zeolites with
solutions containing solvated electrons.56 Species produced K K K
(which are frequently paramagnetic) have been studied by K K K K
ESR spectroscopy and by metal NMR spectroscopy.57 K and
Rb in metal-loaded zeolites have been prepared and studied
by 87 Rb NMR.58
K K K
K K K K
K K K K
K K K
K K K K
K K K
(2)
(1)
3 COMPOUNDS
Alkali metals can also be inserted (intercalated) into
various forms of elemental carbon, particularly of graphite.59 3.1 Introduction
This allotrope has a lamellar structure containing flat cojoined
hexagons of carbon atoms which form flat layers. Such layers, It is apparent from the ionization energy and electronega-
separated by 3.35 A, are not superimposed but alternate, tivity data given in Section 2.3 (Table 1) that the chemistry of
usually in an ABAB pattern, and alkali metal atoms can alkali metal compounds is, with few exceptions, the chemistry
be placed in the gaps simply by treating finely divided of the +1 state. This is, of course, an approximation since total
graphite with weighed quantities of alkali metals (K, Rb, charge separation is unknown, but it is generally believed to
Cs) in an evacuated vessel. Species produced are commonly be a fairly accurate one in the case of the alkali metals. The
of general formula Cx M with x = 8, 24, 36, 48, and 60. matter has been a source of past debate,33,34,61 especially in the
In C8 K, all the layers (now 5.43 A apart) are separated by case of lithium where the high-charge density associated with
layers of K atoms (see (2)), whereas in the other species the small lithium cation can lead to appreciable degrees of
M atoms are found only in each nth interlamellar spacing. polarization of anions. The most modern calculations estimate
Quite typically, lithium behaves differently, giving intercalates that this effect accounts for 10% of bonding at the most, even
such as C6 Li, C12 Li, C18 Li, and others of uncertain and with the most polarizable, least electronegative anions. In the
variable composition such as C15 25 Li and C19 33 Li. All lithium alkyls, for example, the high volatilities, low-melting
such materials are colored (e.g. C8 M bronze, C24 M blue) points, and alkane and arene solubilities often cited in support
and have high conductivity due to fairly ready exchange of of covalent bonding are in fact determined by the strength of
ALKALI METALS: INORGANIC CHEMISTRY 7
bonding between the aggregated molecular units in these com- Table 4 Lattice energies and enthalpies of formation for the alkali
pounds. They say nothing of the bonding of the metal within metal halides
the aggregates. These compounds and their heavier congeners
Lattice energy Hf
are fully discussed in Alkali Metals: Organometallic Chem- Compound (kJ mol1 ) (kJ mol1 )
istry. Other failings of the ionic bond model will be discussed
as they arise. Limits of space preclude a fully comprehensive LiF 1036 147.22
LiCl 853 97.66
treatment of alkali metal compounds but all chemical prin- LiBr 807 83.94
ciples and classes of compound to which the identity of the LiI 757 64.63
metal is relevant will be covered, with appropriate citations to NaF 923 137.10
sources of further information. NaCl 786 98.27
NaBr 747 86.30
NaI 704 68.78
KF 821 135.58
3.2 Binary Compounds KCl 715 104.38
KBr 682 94.12
KI 649 78.37
RbF 785 133.30
3.2.1 Hydrides RbCl 689 104.05
RbBr 660 94.31
The alkali metal hydrides may be formed by direct RbI 630 79.78
combination of the elements. All adopt the fcc structure. CsF 740 132.30
CsCl 659 105.89
The hydride anion is small and thus lattice energies are CsBr 631 94.30
high, especially for LiH with the smallest cation.62 Evidence CsI 604 82.84
for the existence of H in these species came from the
observation of a large increase in conductivity on melting,
and the production of hydrogen at the anode upon electrolysis. 3.2.2 Halides
All react as strong bases and reducing agents. The reaction of
LiH with H2 O has been used as a convenient H2 source, but These, the classic ionic compounds, provide an oft-used
reactivity increases down the group such that RbH and CsH example of periodic trends (see Periodic Table: Trends in the
ignite spontaneously in dry air. The apparent ionic radius Properties of the Elements). All are high melting, colorless
of H varies with the cation, since the electron density crystalline solids. Table 4 shows their enthalpies of formation
around the single proton nucleus is easily polarized (r in and lattice energies. There is a steady decrease in lattice
LiH = 1.37 A, in RbH = 1.54 A). The hydrides find most energies moving down both Group 1 and Group 17, clearly
demonstrating the influence of ion sizes. Size is also important
use in the form of complexes such as Li+ AlH4 , useful as
in dictating crystal packing arrangements67 (see Halides:
selective reducing agents. For further details, see Hydrogen:
Solid-state Chemistry). The comparable sizes of Cs+ and Cl
Inorganic Chemistry.
result in the bcc structure (often termed CsCl structure)
The interstitial hydride [Li8 (H){N(2-pyridyl)Ph}6 ]+
which maximizes the coordination number of each ion at 8,
[Li(Me2 Alt Bu2 )2 ] has been reported.63 Similar hydride com-
whereas a greater size mismatch as in LiCl allows the structure
pound [Li7 (H){N(2-pyridyl)Ph}]6 has also been obtained
to be determined by closest packing of halide ions in a cubic
by further treatment of the above reaction mixture close-packed lattice with the metal occupying the octahedral
with THF. Recently, main-group polyhedral clusters with holes, so giving a mutual coordination number of 6. From this
the Li8 (H) moieties has been synthesized by the reac- hard-sphere ionic bond model, limiting values of cation/anion
tion of a bicyclic 1,3,4,6,7,8-hexahydro-2H -pyrimida[1,2- radius ratios may be calculated geometrically. The successes
a]pyridimine (hpp) in tandem with ZnMe2 and t BuLi. and failures of this model are presented in Table 5. Failures
The product is an ion-separated compound [Li8 (H)(hpp)6 ]+ in the hard-sphere ionic bond model have been ascribed to
[Znt Bu3] , which has been structurally characterized by X- polarization effects, resulting in deformation of the ions. The
ray crystallography. It has shown that the hydride is enclosed overpreponderance of the fcc lattice has been attributed to the
by an unusual (Li+ )8 cubic cage whose six faces are straddled fact that this geometry maximizes any covalent contributions
by the six pyridylamide moieties.64 from p orbitals on the metals. A molecular orbital approach to
Inverse Sodium Hydride, a crystalline salt that contains bonding, treating the lattice as an infinite molecule, would
the reverse H+ and Na formed by reversible encapsulation seem more appropriate where covalent contributions were
of H+ in 36 adamanzane (Adz), has been synthesized thought to be important.
and characterized.65 Theoretical studies of the analogous Trends in enthalpies of formation (Table 4) are not as
Me3 N H+ Na suggest that the species is indeed metastable regular as those of lattice energy. For fluorides, lattice energies
with respect to deprotonation in solvents having dielectric dominate Hf ; therefore the smallest cation gives the most
constants below 2.66 stable fluoride. For the other halides, the ease of production
8 ALKALI METALS: INORGANIC CHEMISTRY
Table 5 Ion radius ratios and predicted and found coordination and ZrF4 -KF has been considered useful in the electrorefining
numbers for the alkali metal halides of Zr and Th metal which would be an alternative and less-
expensive process than the batch-type metallothermic Kroll
r + /r Predicted Experimental
Compound (Pauling radii) CN CN process.6971
LiF 0.44 6 6
LiCl 0.33 4 6
3.2.3 Chalcogenides
LiBr 0.31 4 6
LiI 0.28 4 6
NaF 0.70 6 6 A variety of oxides of the alkali metals are known, illus-
NaCl 0.52 6 6 trating the varying catenation and oxidation states of oxygen.
NaBr 0.49 6 6 Also, they provide some of the rare examples of compounds
NaI 0.44 6 6 where the metals are not, formally at least, +1 cations. All the
KF 0.98 8 6
KCl 0.73 6/8 6 metals form stable salts of O2 , the most stable being Li2 O,
KBr 0.68 6 6 the major product of burning Li in air. All have the antifluorite
KI 0.62 6 6 structure except Cs2 O which has the layered anti-CdCl2 struc-
RbF 1.09 8 6 ture. Peroxide salts M2 O2 are most readily prepared for Li and
RbCl 0.82 8 6 Na but careful oxidation of K, Rb, and Cs allows isolation
RbBr 0.76 8 6
RbI 0.68 6 6 of their O2 2 salts. The paramagnetic superoxides M+ O2
CsF 1.24 8 6 are the major combustion products of K, Rb, and Cs, while
CsCl 0.93 8 8 being unstable for Li and only accessible with difficulty for
CsBr 0.87 8 8 Na. This is a good example of the alkali metal affecting the
CsI 0.78 8 8
route of a reaction by its size/coordinating ability. Among the
more unusual oxides are the poorly characterized sesquioxides
M2 O3 and the red ozonides M+ O3 , also stable only with
of gaseous cations from the metal becomes the main variant
large cations. Interestingly, while the solid lithium ammoniate
parameter; therefore the easily sublimed (low lattice energy of
[Li(NH3 )4 ]+ [O3 ] is isolable, removal of the ammonia causes
the metal), least electronegative Cs produces the more stable
the coordinative demands of the lithium ion to rip apart O3 ,
chlorides, bromides, and iodides. All may be produced by
possibly due to the high-charge density on Li+ . Some inter-
neutralization of aqueous alkali hydroxide or carbonate with
esting suboxides exist for the larger metals, originally thought
the appropriate hydrohalic acid. NaCl (and KCl) are, of course,
to be impure solid solutions of metal and metal monooxide,
available directly from rock-salt deposits or by evaporation
from sea waters. but now fully characterized in the cases of Rb6 O, Rb9 O2 , and
Solubilities are hindered by large lattice energies and helped Cs7 O. For example, Rb9 O2 consists of two Rb6 octahedra
by energy gained in solvent cation binding. Thus, LiF is only sharing a common face (3), each octahedron having a central
sparingly soluble in water (very high lattice energy) while the O atom. Short RbRb distances imply metal metal bonding.
other alkali halides become progressively more soluble with All these species have excess electrons (e.g. Rb9 O2 is better
increasing size (lower lattice energy) and greater solvation represented as (Rb+ )9 (O2 )2 5e ) and hence they have metal-
(more room to bind more solvent molecules). In all cases, lic properties and also show air, moisture, and temperature
highly polar, small molecules (like H2 O and NH3 ) are most
efficient, but LiCl will dissolve in THF, and LiBr and LiI in
alcohols, SO2 , and so on. This chemistry is fundamentally
the coordination chemistry of the cations, and will be covered
more fully later (see Section 4.4.2). Reactions in solution are
generally those of the solvent-separated anions, not strongly
dependent on alkali cation, and are dealt with as reactions of the
halogens (see Fluorine: Inorganic Chemistry and Chlorine, O
Bromine, Iodine, & Astatine: Inorganic Chemistry).
Unusual and interesting reactions of alkali halides have
Rb
been seen in argon matrices by IR spectroscopy. For
example, codeposition of CsF with SOF2 results in the novel
Cs+ [SOF3 ] . An interesting new area of research is emerging
in the study of nanocrystals such as Na14 Cl13 , a tiny fragment
of the rock-salt lattice, whose properties are dominated by
surface effects.68
Solubility and Raman spectroscopic studies of molten
mixtures of ZrCl4 -CsCl, ThCl4 -MCl (M = Li, Na, K or Cs), (3)
ALKALI METALS: INORGANIC CHEMISTRY 9
sensitivity.72 More coverage may be found in Oxides: Solid- of HN3 by neutralization with metal hydroxide or carbonate,
state Chemistry and Oxygen: Inorganic Chemistry. though direct industrial routes to NaN3 have been developed
All alkali sulfides are preparable by reaction of the (e.g. equation 5). Most azides of other elements are made from
metal ammonia solution with sulfur. Exact stoichiometry NaN3 , some finding use as explosives and detonators.
is important to prevent formation of polysulfides.73 Sulfur will
3N2 O + 4Na + NH3 NaN3 + 3NaOH + 2N2 (5)
support combustion of the metals, but products are impure.
All the sulfides M2 S adopt the antifluorite structure and are
susceptible to hydrolysis, giving them the characteristic odor Li1
of H2 S. Hydrolysis is not necessarily complete, however,
and alkali sulfide structures containing coordinated water are
N
known. Reaction of the sulfides with further sulfur produces
N N = Li2
the polysulfides M2 Sx (x = 2 6). As in the oxides, higher
catenation is favored by larger cations. The polysulfides are N
low-melting yellow to red solids. The sodium polysulfides Li1
Na2 Sx (x = 2 5) have significance in their potential use in
battery systems.22 The chemistry and structure of the dianions (4)
in these systems will be dealt with in Chalcogenides: Solid-
state Chemistry and Sulfur: Inorganic Chemistry. For phosphides, a wide variety of stoichiometries are
The selenides and tellurides are similar to the sulfides, being preparable, from simple K3 P to Rb2 P5 to Cs4 P6 , NaP5 ,
preparable from ammonia solutions of the alkali metals. They Na3 P11 , Na3 P21 , Li2 P16 , Li3 P21 , and so on containing complex
are water-soluble yet partially hydrolyzed like the sulfides, catenating anions.76 The alkali metals play little part in the
but are more susceptible to oxidation back to the element. chemistry, so the reader is referred to Phosphides: Solid-state
Not every member of the class Mx Sey /Tey has been fully Chemistry for further information.
investigated, but the many that have promise few surprises (see For the heavier elements As, Sb, and Bi, further diversity
Selenium: Inorganic Chemistry and Tellurium: Inorganic in structure and stoichiometry is found. The ionic bond model
Chemistry). The polonides are similar, and also have their becomes less useful as these species may be thought of
own article (see Polonium: Inorganic Chemistry). as intermetallics, possessing metallic luster, and conduction
or semiconduction properties. Typical examples include
Na3 Bi and NaBi, which becomes superconducting at low
3.2.4 Nitrides, Phosphides, Arsenides, Antimonides, and temperatures (<2.5 K). Further details will be found in the
Bismuthides relevant article for each element, As, Sb, and Bi. Zintl anions
of these elements are also known.77
The most stable of the nitrides, Li3 N, will form
spontaneously from the elements at room temperature. The red
crystalline solid reacts with water to give LiOH and NH3 , and 3.2.5 Carbides
will combust in air. It is handled in an inert atmosphere. The
The alkali metals form only ionic carbides, mostly simple
structure is unique, having two lithiums forming the apices
ionic salts of acetylene, M2 C2 , which liberate acetylene
of a hexagonal bipyramid at 1.94 A and the remaining six in
on reaction with moisture. There has been much recent
a hexagonal array at 2.11 A. These hexagons pack in layers
interest78 in permetalated and hypermetalated hydrocarbon
bridged by the apical lithiums (4). The lithium ions seem to
species, or methanides. Most studied in this respect has been
be mobile in the lattice, making Li3 N an ionic conductor.1
lithium, presumably because of its volatility and amenability
Among the alkali metal nitrides, only Li3 N has been well
to calculation. Mass spectrometric and calculational evidence
characterized. The preparation of the heavier alkali metal
has been presented for CLi6 , CLi3 , and C2 Li4 , but real samples
nitrides has not been successful. However, the preparation
of CLi4 , C3 Li4 , and C5 Li4 are preparable. All are pyrophoric
of Na3 N has been developed recently.74 The anti-ReO3 type
powders. The heavier metals form another class of carbide,
structure of Na3 N has also been determined and it has shown
the graphite intercalation compounds, but as the electron has
that the nitrogen atom is surrounded by six sodium atoms to
not been totally freed from the metal, these were considered
form an octahedron with a Na-N bond distance of 2.37 A. The
in the previous section.
coordination number of the nitrogen atom changes from eight
(in Li3 N) to six (in Na3 N) because the sodium atom has a larger
radius than the lithium atom.75 Convincing evidence for other 3.2.6 Silicides, Germanides, Stannides, and Plumbides
pure alkali nitrides M3 N is absent, but binary compounds of
nitrogen are, however, known for all alkali metals in the form Germanium, tin, and lead give alloy-type binaries of the
of azides M+ N3 . These hygroscopic, ionic salts are amongst alkali metals of variable stoichiometry, but when dissolved in
the most stable of the azides, being fusible with minimal ammonia with the alkali metals they produce colored Zintl-
decomposition. They may be prepared from aqueous solutions type anions (see Zintl Compounds) in solution which can be
10 ALKALI METALS: INORGANIC CHEMISTRY
isolated as crystals with appropriate complexants for the alkali The recent advances in the cluster chemistry of triels
metal. Apart from crystallizing from the molecular solvents, (particularly Ga, In, and Tl) generally recognize the alkali
several clusters can be isolated from the solid-state reactions trielides as traditional Zintl polyanions or nonclassical Zintl
in which direct synthesis of the elements is performed.79 clusters in which an extra electron is present. The alkali
Silicon has not yet been shown to share this behavior in metals form binary and ternary network compounds with
solution but several alkali silicide phases are known,80 with indium and gallium, which are composed of fused clusters
widely variable catenation patterns reminiscent of the sulfides or cluster fragments. In contrast, thallium forms individual
and phosphides, for example, Li7 Si2 , NaSi, Li12 Si7 , and so cluster anions.9597 The alkali metal cations play a decisive
on. The latter contains Si5 6 rings and Si4 12 trigonal planar role in the structure by filling up spaces efficiently and
stars.81 Silicon- and alkali-rich alloy-like phases also exist, keeping the cluster apart.98 Examples of trielide clusters
for example, Na8 Si46 , Li22 Si5 . The rarity of isostructural include anions of Ga11 7 , In11 7 , In4 8 , Tl4 8 , Tl5 7 , Tl6 6 ,
compounds with different alkali metals underlines the folly of Tl11 7 , and so on.99,100 These isolated anionic clusters display
ignoring the alkali cations in compounds of this type. different structures, such as a pentacapped trigonal prism in
A series of alkali tetrelides M12 Tt17 (M = alkali metals; Cs8 Ga11 , K8 In11 , and Rb8 In11 ,99 a three-dimensional indium
Tt = tetrels = group 14 elements), which contain the anionic network built of layers of In12 icosahedra and zigzag chains in
clusters of Tt4 4 and Tt9 4 with the naked cations, have KNa3 In9 ,101 and an arachno 12-vertex polyhedra drums and
been prepared by direct synthesis from the corresponding closo icosahedra in K3 Na26 In48 .102
elements7984 in solid state. Ge9 4 was the first deltahedral
cluster of the tetrels in solid state being isolated and structurally
characterized although the Tt4 4 has been made few decades 3.3 Oxoacid Salts
ago. Single-crystal X-ray structure determination revealed that
The vast majority of the chemistry of alkali metal salts
the unit cell of Rb12 Si17 contains isolated clusters of Si4 4 and
of oxoanions shows little dependency on the identity of the
Si9 4 .82 The Zintl anions Tt4 4 and Tt9 4 isolated from these
cation. Much of the chemistry has been comprehensively
alkalide tetrelides adopt tetrahedral and deltahedral geometry,
covered before,73 and receives further up-to-date coverage in
respectively.7984
the articles on the relevant element. However, a few important
Some other Zintl anions (see Zintl Compounds) of
examples and general points are included here.
Sn9 4 , Pb9 4 such as [K4 Sn9 (18-crown-6)3 ]ethylenediamine,
[Li(NH3 )4 ]4 [Pb9 ]NH3 , [K(18-crown-6)]4 [Pb9 ]en.tol, are
known.8587 The interesting linear, trimer, and tetra- 3.3.1 Borates
mer of rubidium Ge9 clusters [Ge9 =Ge9 =Ge9 ]6 and
[Ge9 =Ge9 =Ge9 =Ge9 ]8 have been synthesized and Alkali borates occur in a few very large Salt-like deposits.
characterized recently.88,89 A great many phases exist, which may be formulated in
equivalents of metal ion, boron oxide, and H2 O, but this
says nothing of structure. The identity of the metal (often
3.2.7 Borides and Others an alkali metal) clearly is one of the determining factors
in the occurrence of a given phase, but these complex
Best known are the MB6 borides, for example, NaB6 ,
matters have their own article (see Borates: Solid-state
comprising an interconnected cubic lattice of B6 octahedra
Chemistry). Most common is borax, Na2 B4 O7 10H2 O, more
with the metal atom at the center of each cube in a CsCl-
informatively written as Na2 [B4 O5 (OH)4 ]8H2 O, which is
like arrangement. Phases M3 B have also been reported, more
used as an alkaline buffer, in glass manufacture, and in fire
saltlike in nature with little covalent BB bonding. The exact
retardants. Its reaction with hydrogen peroxide forms sodium
composition of NaB6 was found to be NaB15 . Recently, the
perborate, Na2 [B2 (O2 )2 (OH)4 ]6H2 O, used as a bleach in
actual phase composition has been found to be Na3 B20 ,90,91
washing powders. This use is declining with lower-washing
and its structural framework consists of interconnected boron
temperatures and the growing use of liquid detergents.
atom icosahedra and additional interstitial boron atoms.92
Mixed-alkali metal polyborates CsLiB6 O10 has been found
So far, the exact compositions and crystal structures of
as a promising nonlinear optical material.103
four alkali metal borides Li2 B6 ,93 Li3 B14 , Na3 B20 ,90,91 and
Na2 B29 92 have been found. Other alkali metal borides such
as potassium, rubidium, or cesium borides have not yet been 3.3.2 Carbonates and Silicates
obtained. Further information is given in Borides: Solid-state
Chemistry. Most alkali carbonates form a wide variety of hydrates, for
Few distinct points arise from discussion of the chemistry example, Na2 CO3 (H2 O)x (x = 1, 7, 10). The decahydrate
of compounds of the alkali metals with the other metallic has pairs of sodiums octahedrally surrounded by water
elements. Most are alloy- or amalgam-like in nature. Whether ligands, with no metal anion close contacts. The paired
they deserve the title compounds has been the subject of octahedra share an edge to give [Na2 (H2 O)10 ]2+ [CO3 ]2 .
debate.94 In contrast, the monohydrate has two independent sodiums
ALKALI METALS: INORGANIC CHEMISTRY 11
coordinated to 5 and 4 carbonate oxygens, respectively. Phosphorus has an even wider range of oxoacid chemistry,
Further variety in structure and stoichiometry is found when and a commensurately wide range of phosphates, phosphites,
carbonic acid acts monobasically to give the bicarbonates, polyphosphates, hypophosphites, and so on of the alkali metals
for example, NaHCO3 , which also form a variety of hydrates, are preparable. Sodium and potassium are the most common
as well as mixed carbonate/bicarbonate systems, notably cations used, largely because of their availability and low
the major natural carbonate trona Na2 CO3 NaHCO3 2H2 O. cost. The cation often has little effect on the properties and
Similar behavior is found for other alkali metals and applications, which are covered in Phosphates: Solid-state
indeed mixed-metal phases are common, for example, Chemistry. Most form a variety of crystalline hydrates, which
K2 CO3 Na2 CO3 6H2 O, KLiCO3 , and so on. Lithium forms no have been well covered in previous treatments73 and need
bicarbonates. Its carbonate is rather insoluble in water, and is not be repeated here. True to form, lithium is the exception,
easily prepared anhydrous. All the carbonates are susceptible forming no stable hydrates with phosphorus oxoanions.
to thermolysis (equation 6). The temperature required for this A variety of alkali arsenic oxides has been isolated,
reaction increases with increasing cation size. This periodic including Na2 HAsO4 , NaH2 AsO4 , RbH2 AsO4 , LiAsO3 ,
trend is shared with other oxoanion salts since the lattice KAsO3 , NaAsO2 , NaAsO3 , Na3 AsO3 , and Na3 AsO4 . Some
energy of the product oxide is the dominant factor. find use as wood preservatives, bacteriocides, and herbicides.
Hydrates are common. Many are salts of the poorly
M2 CO3 M2 O + CO2 (6) characterized arsenious acid As(OH)3 ,104 but salts of arsenic
acid, H3 AsO4 , are also known. They are good oxidizing
It will be seen in the article Zeolites that the chemistry agents. Structures are complex, with polymeric anions being
of the metal ion is often unimportant in their complex common (cf. phosphates). The identity of the metal can affect
structures. Consequently, there is little to discuss in terms of the catenation mode of the anions, for example, LiAsO3 has
periodic trends and differences. It should be noted, however, a dimeric repeat-unit in its infinite chains of AsO4 tetrahedra,
that sodium silicate is important for its use as a builder in while NaAsO3 has a tetrameric repeat-unit, and KAsO3 has a
washing powders. cyclic trimeric anion As3 O9 3 .
There is a greater tendency to salts of SbV over SbIII .
NaSb(OH)6 , NaSbO3 , LiSbO3 , and Li3 SbO4 are all known.
3.3.3 Oxoacid Salts of Nitrogen, Phosphorus, Arsenic, Polyanion motifs are again common. While Bi(OH)3 forms
Antimony, and Bismuth no anions, being basic, Biv oxoanions are rare and very
strongly oxidizing. However, NaBiO3 , prepared from Bi2 O3
All alkali metals form nitrates MNO3 and nitrites MNO2 . and Na2 O2 , is sold as a powerful oxidant, and has an ilmenite
The former decompose to the latter with strong heating in structure. Hydrates are also known.
the absence of O2 . This tendency is greatest for the smaller
metal ions, following a group trend. All are hygroscopic and
crystalline hydrates are common. 3.3.4 Oxoacid Salts of the Chalcogens
The nitrates are prepared by neutralization of nitric
acid with the appropriate hydroxide. In some cases, The chemistry of polonium may be discounted because of
metathesis reactions have been commercially exploited the short half-life and extreme rarity of the element. Tellurates
(equation 7). Through manipulation of the differing aqueous are mostly salts of telluric acid, Te(OH)6 , and are not similar to
solubility/temperature relationships of the various salts in the the sulfates. Selenates are more similar, forming compounds
equilibrium mixture, KNO3 is isolable. such as Na2 SeO4 (10H2 O) exactly like sulfur, but the chemistry
is not so extensive as to define the role (if any) of the alkali
NaNO3 + KCl
KNO3 + NaCl (7) metal in the compound. The extensive oxo chemistry of sulfur,
however, allows such comparisons to be drawn. For example,
The nitrites are preparable thermally as mentioned above, both RbHSO3 and CsHSO3 are isolable, while the salts of the
or by reaction of nitrogen oxides with metal hydroxide or smaller cations produce the disulfites M2 S2 O5 . The full variety
carbonate (e.g. equation 8). The nitrites are all water-soluble is too rich to explore here (see Sulfur: Inorganic Chemistry)
but with a smaller tendency to hydrate formation than the but the great industrial importance of Na2 SO4 in the paper and
nitrates. NaNO2 is used as an oxidant and a nitrogen source cardboard industry should be noted.
in the production of azo dyes, and so on. It has also found
wide use in curing meats, although recent concern has been
expressed over the safety of the products of the reactions of 3.3.5 Oxyhalides
NO2 with the organic compounds in foods. Salts of other
nitrogen oxoacids exist, for example, Na4 N2 O4 and Na3 NO4 , Those oxyhalide anions that find use are most often used
and these receive coverage in Nitrogen: Inorganic Chemistry. as alkali metal salts. A particular metal is often chosen to
optimize physical properties; for example, LiClO4 is used
Na2 CO3 + NO + NO2 2NaNO2 + CO2 (8) as an oxidant in rocket propellants because the light metal
12 ALKALI METALS: INORGANIC CHEMISTRY
maximizes energy density, while the larger ion in KClO3 3.4.2 Amides
gives the nonhygroscopic properties that are desired for use in
safety matches and pyrotechnic displays. The metal has little The metal ammonia solutions discussed in Section 2.4
chemical effect on the anions; indeed, a structure determination are metastable. Their decomposition, catalyzed by transition
metal ions, yields the ionic salts M+ NH2 . They may also
on NaClO3 was used to define the precise geometry of the
be formed by passing ammonia gas over the heated molten
isolated ClO3 anion.105
metals. They are only sparingly soluble in ammonia, and
Periodic trends are apparent, again due to size effects
decompose on contact with moisture. NaNH2 (sodamide)
in crystal packing. The very soluble LiClO4 crystallizes
has historically been widely used as a very strong base in
from water as a trihydrate with each lithium surrounded
anhydrous media in organic synthesis. It also serves as a
by face-sharing octahedra of water molecules which weakly source of the NH2 nucleophile. Where this second mode of
hydrogen-bond to the poorly coordinating perchlorate ions.106 reactivity is undesired, it has largely been superseded by the
In CsClO4 , however, the sparingly soluble salt crystallizes stronger, more soluble, less nucleophilic dialkylamide bases,
anhydrous from aqueous solution in a BaSO4 -type structure. such as lithium diisopropylamide (LDA) (see Section 5). The
Further examples may be found in the relevant chapters on sodium and potassium counterparts of LDA was found to be a
halogen chemistry. better reagent over the metallation of diphenylmethane.107,108
Structurally, the alkali amides behave as simple ionic salts.
All have high-temperature modifications where the anions are
3.4 Some Salts of Other Inorganic Acids freely rotating pseudospheres. NaCl-type lattices are found for
high-temperature potassium, rubidium, and cesium amides.
The low-temperature forms are distorted close-packed lattices
3.4.1 Hydroxides due to the asymmetry of the NH2 anions.109
By using a combination of gas-phase synthesis and
The alkali hydroxides are the strongest bases accessible millimeter/submillimeter-wave spectroscopy, LiNH2 was
in aqueous solution, since the alkali metals are the most found to be a monomeric unsolvated planar molecule. The
electropositive elements in the Periodic Table. NaOH and lithium amide {[H2 NCH2 CH2 N(H)Li] } has a polymeric
KOH are made and used on a massive scale industrially, as ladder structure with two types of (NLi)2 ring which alternate
well as being ubiquitous laboratory reagents. They are able to throughout its infinite length.110
deprotonate even weak carbon acids such as cyclopentadiene Superbases react readily with organic substrates to
when poorly donating anhydrous reaction media are employed give heavy metal derivatives of the substrate function as
(the reaction produces water which can then solvate the exceptional strong proton abstraction reagents in organic
excess hydroxide, thereby providing a driving force). All are synthesis. The lithium amide-alkoxide complex is com-
hygroscopic to varying degrees, and form numerous hydrates. posed of four LiNLiO units, whereas the bimetallic
Lithium hydroxide has the lowest tendency to hydrate, since lithium/heavier alkali metal mixed amide-alkoxide com-
plexes are constructed from Lix My Na Ob units (x + y =
the small hydroxide ion can pack efficiently with the lithium
a + b). The trimetallic Li-Na-K amide-alkoxide compounds
cations (cf. perchlorates). It forms a stable, nondeliquescent
consist of a twelve-vertex Li2 Na2 K2 N4 O2 cage as in
monohydrate that can be easily dehydrated by vacuum or heat.
[{RN(H)2 (But O)[LiNaK(TMEDA)2 ]2 }] has been reported.111
It is also the weakest base in the gas phase, where it exists
predominantly as ring dimers. Base strength increases down
the group, as the hold of the metal on the hydroxide becomes 3.4.3 Alkali Pseudohalides
weaker. In aqueous solution, of course, there is little difference
between the basicity of the alkali hydroxides due to the effects The salts of hydrazoic acid, M+ N3 , have already been
of solvent leveling. discussed in Section 3.2.4, but a variety of other alkali
All the hydroxides absorb CO2 from the air to form pseudohalides exist. The most important of these are the
carbonates. Similarly, formates may be prepared by heating cyanides M+ CN , preparable by neutralization of HCN with
solid hydroxides with carbon monoxide (e.g. equation 9). the appropriate alkali base. NaCN and KCN reached such
industrial importance that alternative bulk syntheses have been
developed (e.g. equation 10). This Castner process fed the gold
180 C extraction industry and continued to feed the electroplating
NaOH + CO HCO2 Na (9)
and nylon synthesis markets until cheaper routes directly
to HCN were found. In cases where the alkali cyanides
are still required, the simple neutralization route is now
The hydroxides are formed by electrolysis of aqueous
most economic.
brines as part of the chloralkali process. The metal formed
at the cathode immediately reacts with water to produce the 1/2H2 600 C 1 800 C
hydroxide and hydrogen gas. Na + NH3 NaNH2 Na2 CN2 NaCN (10)
+C 2 +C
H2
ALKALI METALS: INORGANIC CHEMISTRY 13
Structurally, the alkali cyanides are truly pseudohalides, greater effect on the reactivity of the compound. The nature of
all except LiCN adopting either NaCl or CsCl structures at the structural origins of such differences will be discussed in
normal temperatures. The required high symmetry is produced Section 4. Apart from specialty uses in organic (and inorganic)
by rapid solid-state fluxionality in which the CN dumbbell syntheses, NaBH4 is widely used in the bleaching of wood
ions rotate to sweep out a sphere of radius intermediate pulp and in chemical plating of metals such as nickel on to
between those of Cl and Br . Low-temperature phases nonmetal surfaces.
exist112 where this fluxionality is not present, for example,
500 C
CsCN. Once again, lithium is the exception, exhibiting a fully Na2 B4 O7 + 7SiO2 + 16Na + 8H2 4NaBH4 + 7Na2 SiO3 (12)
ordered but loosely packed structure related to zinc blende in
4NaH + BCl3 NaBH4 + 3NaCl (13)
which each lithium has three N contacts and one C contact. A
preference for N coordination is rare among those compounds 4LiH + BF3 OEt2 LiBH4 + 3LiF + Et2 O (14)
where it is possible to distinguish between C and N. The highly
polarizing cation seems to distort the anion, its CN bond The heavier congeners M+ EX4 (E = Al, Ga, In) are
length being 1.15 A in LiCN but 1.05 A in NaCN. The variety progressively more reactive. The most common, LiAlH4 , has
of possible bonding modes of CN (linear, bent, 2 , 1 , 2 , been widely used as a reducing agent and hydrogenating
etc.) in less aggregated forms of M+ CN has been the subject agent. It is a more potent reductant than the borohydrides and
of calculational113 and gas-phase and matrix IR investigation, is more soluble and hence more reactive in ethers. This greater
but solid-state data at present are limited to a few crown reactivity makes LiAlH4 less selective than borohydrides and
complexes and complex transition metal cyano anions. makes handling under an inert nitrogen atmosphere advisable.
Other alkali pseudohalides may be prepared from the It is much used as a rigorous drying agent in laboratory solvent
cyanides. Mild oxidation of M+ CN in solution with lead distillations, especially of ethers. The bonding in LiAlH4
oxides produces M+ OCN . The heavier chalcogens may be may have appreciable covalent character since the crystal
directly combined (e.g. equation 11). packing is not a simple close-packed arrangement115 and
contains some short LiH distances [4LiH = 1.88 2.00 A,
1LiH = 2.16 A, cf. (Li+ H ) = 2.04 A ].
KCN + S KNCS (11)
Complex hydrides are known for transition metals
also. Evidence has been presented115 suggesting substantial
Potassium thiocyanate, like others in the series, a soluble covalency in the WH Li bonds of [W(PMe3 )3 H5 Li]4 (5).
and hygroscopic ionic salt, finds use in photographic
developers. KNCSe may be similarly prepared.114 The TeCN
anion is only isolable with very large organic cations, and so H H H H
no solid alkali tellurocyanate is known. Metastable solutions (Me3P)3 W Li .. H W(PMe3)3
of M+ TeCN may, however, be prepared. HH H H H
Li Li
when crypt ligands (see Section 4.3) are introduced to shield 4.2 General Principles
the anion from the alkali metal a regular tetrahedral form
is resumed.117 HMPA solutions of sodium can reduce these The coordinating ability of the alkali metals generally
complexes even further, so that formally M3 transition metals decreases with charge density in the sequence Li > Na >
are formed. However, in these highly shock-sensitive and K > Rb > Cs but molecular recognition arguments may
pyrophoric materials the electrons are almost certainly spread sometimes dictate a different order (see Section 4.3). The
on to the carbonyl ligands and perhaps on to the alkali metals predominance of ionic bonding removes the directional
themselves.118 The extreme reducing power of HMPA/Na constraints often seen in transition metal complexes, and
solutions stems from the presence of sodide Na(HMPA)x therefore geometries vary widely, depending upon the
anions. Typical examples of these superreduced species minimization of interligand repulsions and the maximization
include Na3 Re(CO)4 and Na3 V(CO)5 . of contacts from metal to electronegative center. For the larger
metals, extensive polymerization often ensues where it is not
hindered by the use of chelating ligands (most notably in the
O
case of crowns and crypts) or very bulky ligands. However,
K O O in some cases this tendency to polymerize may be limited by
O C O O judicious choice of appropriate ligands and synthetic route.
C Fe K C The smallness of lithium in comparison to most anions makes
C
O C C Fe C this tendency to limited oligomerization most prevalent for
K OO O C O K that metal (exemplified in the hexameric, molecular nature of
O (nBuLi)6 , cf. (nBuNa) ; see Alkali Metals: Organometallic
K Chemistry). Molecular aggregates containing up to 20 lithium
(6) cations have been prepared,119 but dimers are most common,
and solid-state monomers are comparatively rare in the
absence of highly chelating ligands.120
Coordination numbers are so dependent on ligand geom-
etry that the concept of preferred coordination number is
4 COORDINATION COMPOUNDS of limited use. For example, lithium may be said to prefer
4 coordination, but examples of 1 to 12 coordination are
known. Low formal coordination numbers are often accompa-
4.1 Introduction
nied by secondary interactions with other sources of electron
All alkali metal-containing materials have close contacts density, such as CH bonds and arene -systems. There are
from the metal to another atom, or group of atoms, and even examples of CH activation caused by a low-coordinate
to this extent all compounds may be termed coordination sodium cation.121 Of course, there is a trend towards higher
compounds. However, the term is usually reserved for those preferred coordination for the heavier group members (6 for
compounds containing a metal coordinated to a neutral ligand, Na, K; 8 for Rb, Cs).
normally (but not necessarily) one containing organic func-
tions. The coordination chemistry of the alkali metals has in 4.3 Macrocyclic Complexes
the past been viewed as a rather poor area of research. Their
unipositive charge and relatively large size gave the met- The serendipitous discovery by Pedersen of the crown
als a rather poor coordinating ability. Consequently, aqueous ether ligands122 sparked the development of what is now
coordination chemistry often gave only hydrates, with a few a systematically and intensively investigated, and well-
examples of salicylates and diketonates, rendered stable by reviewed,123,124 field. The crowns are cyclic polyether
the chelate effect. However, interest and systematic study has molecules containing a variable number of oxygen atoms
blossomed over the last 20 years, largely because of two phe- (commonly 4, 5, or 6) linked by (normally) ethylene (e.g.
nomena. The first was the Nobel prize-winning discovery of 18-crown-6, (7)) or 1,2-dibenzo bridges (e.g. dibenzo-14-
the crown ethers and their development into the field of molec- crown-4, (8)). These ligands wrap around the metal, and
ular recognition, making use of the macrocyclic effect in can displace water ligands due to the entropically dominated
overcoming the low charge density of the heavier alkali met- macrocyclic effect. The resultant organic sheath around
als. The second is the increased investigation of nonaqueous the cation confers solubility in organic solvents which leads
alkali metal chemistry, triggered largely by the growing impor- to uses in phase transfer catalysis. The coordination of the
tance of lithium in organic synthesis. Few ligands are superior cation by the crown weakens its interaction with the anion,
to water in their ability to coordinate to alkali metals, but by sometimes to the point of total separation. The substantially
excluding H2 O and limiting the supply of available Lewis base increased nucleophilicity of the anion then leads to much more
donor molecules, a rich structural chemistry has developed, rapid reaction (the naked anion effect). The discovery of the
challenging that of the transition metals in its diversity. crown ethers also sparked the development of research into
ALKALI METALS: INORGANIC CHEMISTRY 15
molecular recognition, since the crown ether host could as effectively as valinomycin is known to do, but Nature is
recognize specific alkali metal (and other) cation guests due ingenious: the amide units engage in reversible, intramolecular
to the fixed size of the macrocyclic cavity. The different ionic hydrogen bonding to sew-up the cycle in a tennis-ball
radii of the M+ ions induced the selective complexation effects seam arrangement, having the combined effects of making
that form the basis of the use of crowns in cation separation, the cavity smaller, making it three-dimensional (cryptand-like)
and recently in ion-specific measurement devices.125 The and presenting the hydrophobic isopropyl groups to the outside
crown ethers, tribanzo-21-crown-7 and tetrabenzo-24-crown- of the molecule and so allowing good transport through lipids.
8, are found to exhibit modest selectivity for Rb+ and Cs+ It is this flexibility which makes valinomycin effective; its
over other alkali metal ion, respectively.126,127 avidity and selectivity generated by its three-dimensionality is
accompanied by the facile complexation and decomplexation
kinetics that are essential for efficient transport. While the
O cryptands possess the former characteristics, the reliance
O O O O on inflexible covalent linkages to achieve them make the
ion uptake and (especially) release kinetics unsuitable for
a transport function. The synthetic answer came with the
O O O O development of the lariat ethers,130 which are crown ethers
O with additional Lewis base donor side-arms that mimic
the natural system by giving reversible three-dimensional
(7) (8)
incarceration of the alkali metal ion upon complexation.
This Na+ /K+ selectivity is of paramount importance since 4.4 Other Complexes
many physiological functions depend upon its maintenance.
The selective transport of K+ across cell membranes is 4.4.1 Introduction
achieved by the natural antibiotic valinomycin (10), which
contains a crownlike cycle of ether oxygens, but also a number It was said in the preceding section that highly chelating
of amide linkages. The cycle would seem too large to bind K+ ligands can exclude water from the coordination sphere of
16 ALKALI METALS: INORGANIC CHEMISTRY
Li (15) (16)
Li
Br Li Nonmacrocyclic complexes of other alkali pseudohalides
are rare indeed, though many other inorganic anions are found
Li
in alkali metal complexes. Oxoanion salts, such as LiNO3 ,
are found to form complexes. The binding mode of the anion
in such cases would be expected to be highly dependent
(13)
on the nature of the base employed, and this is found to
be the case. In dissolution syntheses, 2-methyl- and 3,5-
4.4.3 Complexes of Other Inorganic Anions dimethylpyridine gave polymeric LiNO3 (L)2 and monomeric
LiNO3 (L)3 complexes, respectively. In the polymer, links
The largest contiguous group of nonmacrocyclic, molecular were through bridging bis 1 nitrate oxygens, while the
complexes is provided by the alkali thiocyanates. The monomer contained only one nitrate Li contact.148
HMPA complex of lithium thiocyanate crystallizes as an Complex hydrides give a variety of interesting structures.
unusual asymmetric dimer. The sodium complex of the For LiBH4 derivatives, a monomeric example crystallized
same stoichiometry exists in a more normal symmetric dimer from THF149 shows three BHLi bridges and a very short
arrangement, while the potassium thiocyanate complex adopts BLi distance of 2.19 A (cf. CLi, 2.36 A in the analogous
an unprecedented trimeric arrangement.146 The thiocyanate (-H)3 C environment of solid (MeLi) ). However, when
prefers a terminal, N-bonding mode in all these complexes, TMEDA is used as the donor in the parent borohydride,
although solution evidence exists for a 2 N-bridging mode a dimeric complex (16) results, containing four 2 and
in the complex LiNCSTMEDA, dimeric in solution. In two 3 BHLi contacts.150 A tetrameric complex with 4
18 ALKALI METALS: INORGANIC CHEMISTRY
BH(Na)3 bonds was obtained from a diethyl ether solution of R project orthogonally from the Li2 N2 ring plane (17), thus
NaBHMe3 . This could also be considered as a lattice fragment preventing vertical association. However, when the R groups
of sodium hydride where each metal is coordinated by one are small and restricted, lateral association (laddering, (18))
Lewis base (Et2 O), and each hydride coordinates one Lewis of rings results.153,154 Polymerization in this way can lead to
acid (Me3 B).151 amorphous materials, as for piperididolithium, (C5 H10 NLi) ,
This list of examples could contain complexes obtained but a soluble, oligomeric precursor (19) to infinite laddering
from a very wide variety of alkali metal compounds has been isolated in this case.156 Lithiation of the terminal
where lattice energy considerations make complex formation piperidine ligands would result in completion of the ladder
thermodynamically favorable. The in situ preparative routes structure. A bend is discernible in this ladder structure of (19),
even make trapping of kinetic, as opposed to thermodynamic, which in hexamethyleneiminolithium (20) has increased so
products feasible. Furthermore, complexation can stabilize a that both ends of the ladder meet in a six-membered cycle.153
compound unknown in the uncomplexed state. (For example, The original Li2 N2 dimers may still be discerned as being
it was stated in Section 3.2.3 that the heavier alkali metals connected by the shortest LiN bond lengths.
favor higher catenation in sulfides. Consequently, Li2 S2 is
the most highly catenated parent lithium sulfide known, but
the complex Li2 S6 (TMEDA)2 is preparable by a number of
routes.152 ) While there are many such complexes not covered R Li R
N Li N Li
here, and doubtless many more to be discovered, no further N N
major structural or bonding trends in this section remain to R R Li N Li N
Li
be discussed at this still comparatively early stage in the
development of alkali metal coordination chemistry.
(17) (18)
5 METAL-ORGANICS
H
N N N
Those compounds with metal carbon bonds that fit the N Li Li H
H Li N
strict definition of the term organometallic deservedly have Li
N N N H
their own article in this encyclopedia (see Alkali Metals:
Organometallic Chemistry), but a large and important class
of compounds exists that contain organic groups bound
to noncarbon central anions that give the compounds a
(19)
molecular character distinct from the latticelike behavior
of most of the inorganic salts discussed previously. This class,
which for the purist may be described as metal-organics
rather than organometallics, is briefly discussed here.
When R and R are large and/or floppy, this laddering is less R THF THF
favorable. In the exceptionally bulky case of [LiN(SiMe3 )(2,6- THF O K
i-Pr2 C6 H3 )]2 , a simple dimer is most stable,157 but normally R Li R K
R O R
ring size increases in order to distance the N centers from each O O O K
K O
other and symmetrize charge distribution around Li. Thus, Li O R
LTMP forms a cyclic tetramer, virtually linear at lithium, R K
K O THF
while LHMDS forms a trimer.153 LDA exists in nondonating
THF THF R
solution as cyclic oligomers and normally precipitates as an
amorphous polymer, but crystallizes from hexane/TMEDA as (21) (22) R = t-BuC( CH2)
a polymeric helix.158
The effect of solvation by Lewis base donor solvents is to
reduce this complexity. THF, the most widely used solvent state due to the longer KO bonds.163 Similar aggregated
for these bases, forms bis-solvated dimeric complexes with species have been observed in solution.162
most amidolithiums, since this smallest Li2 N2 ring provides Mixed-metal enolate has also been found. The core of the
maximum room for the additional donor molecules. Chelating lithium sodium enolate of pinacolone forms an open stack
donors may even produce monomers, but ion separation is structure in which two edges of the face-sharing cubes are
found in the solid state only when the anion is stabilized by absent.164
electron-accepting heteroatoms.159
5.3 Others
5.1.2 Amides of the Other Alkali Metals
Of the vast plethora of alkali-organic structures,61,165 a few
The longer bond lengths of the heavier alkali amides groups deserve special mention, even if they have yet to find
remove the constringent aggregation patterns of lithium the widespread synthetic significance of the above two classes.
chemistry.154 Variety abounds, and too few data exist to
draw convincing generalizations about uncomplexed amide
geometries. Above it was noted that LiHMDS was trimeric Li X
in the solid state; NaHMDS is an infinite chain polymer,
but KHMDS is a dimer.160 Other rule violations include X Li
the stacked amide structures of (Me2 NNa)10 (TMEDA)4 and X Li
(Me2 NNa)12 (TMEDA)4 .161 However, in these and most Li X
X Li
other known structures, the M2 N2 subunit dominates in both Li Li X
complexed and uncomplexed amides. X X
Li X Li
The heavier alkali amides have yet to find widespread use X Li
Li X
in synthesis owing to the inferior selectivity imparted by their X
greater reactivity. However, in situ mixtures of heavy alkali Li Li X
Li X
alkoxides and lithium amides are finding increasing use as
very strong bases.6,155 The nature of the reactive species is as (23) (24)
yet unclear.
The imidoalkalis, RR C=NM, are important because it
5.2 Alkali Metal Enolates was in the attempt to explain their structures that the
widely applicable stacking principle was developed.153,154
These form a class of compounds which has received much The uncomplexed lithium cases, for example, LiN=C(t-Bu)2 ,
study because of their part in the important CC bond-forming form hexameric structures, that is, double stacks of trimers
aldol reaction.162 The primary structural units are again rings (23). Further stacking is precluded by the bulky R groups.
but here association is vertical (stacking) rather than lateral, If both of these are flat, for example, Ph, infinite stacking
since the organic groups can align themselves in the same (24) results in precipitation of amorphous powders. One such
plane (approximately) as the (LiO)x rings (see (21)). The material, (LiN=CPh2 ) , can be broken down by pyridine
uncomplexed lithium enolate of pinacolone is a stack of two to a double stack of solvated dimers (25). For bulky donors
trimers but shrinks to a stack of two dimers when solvated by (e.g. HMPA) and imines, only the simple dimer can form, for
THF. The sodium enolate of pinacolone crystallizes with one example, (t-Bu2 C=NLiHMPA)2 . No uncomplexed heavier
unenolized ketone per metal; therefore it also forms a four- imidoalkali has yet been prepared crystalline, except as a
metal stack of two bis-solvated dimers. In contrast, the THF constituent of mixed-metal species Li4 Na2 (N=CRR )6 . These
complex of potassium pinacolonate (22) can accommodate have the same stoichiometry as the double-stacked trimers in
donor molecules while maintaining the higher aggregation which each lithium attains three coordination, but the structure
20 ALKALI METALS: INORGANIC CHEMISTRY
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Alkali Metals: 3/2, both of which are NMR active. Organolithium compounds
enriched in 6 Li have also been prepared and studied by NMR.
Organometallic Chemistry Lithium NMR data are used to determine structural and
bonding information about organolithium compounds, and
variable-temperature NMR studies are specifically useful in
Melanie J. Harvey elucidating dynamic exchange processes that occur with these
University of Saint Mary, Leavenworth, KS, USA molecules (see Stability Constants & their Determination).
Lithium chemical shift values are used to distinguish contact
Based in part on the article Alkali Metals: Organometallic Chemistry ion paring from solvent-separated ion paring and also the
by Charles M. Lukehart which appeared in the Encyclopedia of degree of covalency in LiC bonds (increased covalency
Inorganic Chemistry, First Edition.
shifts lithium resonances to lower field). The magnitude of
JLiC coupling is used as a more direct measure of the degree
1 Introduction 1 of LiC bond covalency. UV-Visible spectrophotometry also
2 General Aspects of the Chemistry of Organoalkali provides important information about ion paring in solutions
Metal Compounds 1 of organolithium compounds.
3 Alkyl, Alkenyl, Alkynyl, and Aryl Compounds 3 Theoretical calculations of organolithium species have
4 Allyl, Pentadienyl, and Benzyl Compounds 7 received considerable attention. The low atomic number
5 Cyclopentadienyl and Related Compounds 8 of lithium is suitable for the most sophisticated molecular
6 Hydrocarbon Radical Anion and Dianion orbital methods. Although much debate exists over the degree
Compounds 9
of covalency within lithium carbon-bonding interactions,
7 Related Articles 9
the presence of some covalent character in LiC bonds of
8 Further Reading 9
alkyllithium compounds is widely accepted.
9 References 9
The bonding interactions within organoalkali metal
complexes of the heavier alkali metals are generally considered
to be strongly electrostatic or ionic in nature. This is supported
by a large collection of evidence, consisting primarily of
solution NMR data, single-crystal X-ray analyses, and gas-
1 INTRODUCTION phase computational studies.
(equation 1). Relatively acidic organic molecules will react directly with
alkali metal hydrides. Crown ethers, strong amines, or ether
2M + RX RM + MX (1) donors are often used in reactions with the heavier alkali metal
hydrides to give more soluble organometallic products. This
This route is useful for the synthesis of organolithium synthetic route has become increasingly less common due to
compounds, but is often hindered with the more reactive and the generally low solubility of organoalkali metal products
heavier alkali metals because of the tendency toward Wurtz and marginal purity of alkali metal hydrides.
coupling (equation 2). The reaction of an organo- or amido-alkali metal reagent
with an acidic organic molecule produces an organoalkali
RM + RX RR + MX (2) metal compound and the amine or organic compound
(equation 7).
The formation of the metal halide as a by-product limits the
use of this method for the synthesis of reagents intended for RM + R H R M + RH (7)
further reactions. The relative solubilities of the organoalkali
metal compounds and the metal halides formed in these Methyl lithium and butyl lithium are widely used for the
reactions do not generally allow for easy separations. synthesis of other organolithium compounds. For example,
The assay of organoalkali metal reagent solutions can be lithium cyclopentadienides are generally prepared by the
performed using hydrolysis (equation 3), followed by simple reaction of the cyclopentadiene with butyl lithium. In
acid base titration (equation 4). contrast, the amido-alkali metal compounds are becoming
increasingly important in the synthesis of organoalkali
RM + H2 O RH + MOH (3) metal compounds with the heavier alkali metals. For
MOH + HCl MCl + H2 O (4) example, 1,2,4-tris(trimethylsilyl)-1,3-cyclopentadiene reacts
with potassium bis(trimethylsilyl)amide to form potassium
1,2,4-tris(trimethylsilyl)cyclopentadienide.8
2.1.2 Metallation
an organolithium compound. In fact, the reaction of a heavier solution and in the solid state will be discussed in following
alkali metal alkoxide with an organolithium compound is the sections.
most widely used method for preparing organoalkali metal
compounds of the heavier alkali metals (equation 11). For 2.3 Reactivity
example, 1,3-bis(trimethylsilyl)allyl potassium was prepared
by the reaction of 1,3-bis(trimethylsilyl)allyl lithium with In general, the reactivity of the alkali metals and
potassium t-butoxide (equation 12).11 This reaction was the reactivity of the organometallic compounds of these
effected in hexanes with additional TMEDA. The allyl metals increase as we go down the group or column.
potassium compound is insoluble and can be isolated Organoalkali metal compounds are similar to, but more
by filtration in high yield. In general, these reactions reactive than Grignard reagents. For example, the carbanions
are performed in hydrocarbon solvents with some ether of organoalkali metal compounds have been widely used as
present. The alkoxide is generally chosen for easy separation nucleophiles in reactions with various electrophilic organic
following the reaction. Organostannanes can be reacted compounds. Organolithium compounds have been particularly
with phenyllithium to give tetraphenyl tin and a different useful in this way for the formation of new carbon carbon
organolithium compound12 (equations 13 and 14). bonds. Organoalkali metal compounds are both air- and
moisture-sensitive and are sometimes pyrophoric. In addition,
LiR + MOR MR + LiOR organoalkali metal compounds will react as Brnsted bases
(M = Na, K, Rb, Cs) (11) with protic reagents.
There are a couple of other general features of the
Li[C3 H3 (SiMe3 )2 ] + KOC(CH3 )3 K[C3 H3 (SiMe3 )2 ]
reactivity of organoalkali metal compounds worth mentioning.
+ LiOC(CH3 )3 (12) (1) Most organoalkali metal compounds form complexes
4PhLi + (H2 C=CH)4 Sn Ph4 Sn + 4H2 C=CHLi (13) with crown ethers, provided the crown is an appropriate
Ph3 SnCH2 AsPh2 + PhLi Ph4 SnCH2 AsPh2
size for the particular alkali metal (see Alkali Metals:
Inorganic Chemistry). (2) In general, the thermal stability
+ Ph2 AsCH2 Li (14)
of organoalkali metal compounds decreases as their size
and reactivity increases. Both - and -eliminations are
2.1.4 Carbometallation usual pathways of thermal decomposition for group 1
organometallic compounds.
The electropositive nature of alkali metals allows for
insertions into alkali metal carbon bonds. Thus, the reaction
of an organoalkali metal reagent with an unsaturated organic
molecule produces a more complex organoalkali metal 3 ALKYL, ALKENYL, ALKYNYL, AND ARYL
compound. In particular, organolithium compounds will COMPOUNDS
react in this way with conjugated dienes, even under mild
conditions. For example, 1,3-butadiene reacts with tert-butyl
lithium to give an allyl lithium compound3 (equation 15). 3.1 Alkylalkali Metal Compounds
In recent years, considerable attention has been
(CH3 )3 CLi + H2 C=CHCH=CH2
given to organoalkali metal compounds containing bulky
(Z and E)-(CH3 )3 CCH2 CH=CHCH2 Li (15) silicon-substituted alkyl groups. The use of these ligands
has provided compounds that differ dramatically in structure
2.1.5 Thermolysis and Thermal Rearrangements and reactivity from compounds with smaller alkyl groups.
Organometallic compounds with bulky silicon-substituted
Organolithium compounds can be converted to other alkyl groups have been reviewed.17
organolithium compounds under high temperatures. For
example, dilithiomethane is produced from methyl lithium
3.1.1 Synthesis
when heated between 223 and 226 C.13
Most alkyllithium compounds are prepared by the direct
2.2 Structure synthesis method shown in equation (1). For example, lithium
metal reacts with bromomethane in ether to form methyl
The structures of organolithium compounds have been lithium and lithium bromide (equation 16).2
extensively studied, and there are a number of reviews
available.1416 A recent review of the structures of organoalkali 2Li + CH3 Br LiCH3 + LiBr (16)
metal compounds of the heavier group 1 metals has also been
made available.1 Specific details of the structures formed The heavier alkylalkali metal compounds can be prepared
by various types of organoalkali metal compounds both in from a transmetallation reaction with an alkyllithium
4 ALKALI METALS: ORGANOMETALLIC CHEMISTRY
compound. For example, methyl potassium is formed from bonding and crystallize in a nickel arsenide-type lattice.30 Tert-
the reaction of methyl lithium with potassium t-butoxide butyllithium also exists as a tetramer in the gas phase26 and in
(equation 17).18 hexanes or benzene.31,32 Aggregation energies and conformer
preferences have been investigated for tert-butyllithium using
MeLi + tBuOK MeK + tBuOLi (17) density functional theory.33
The synthesis, structures, and reactions of silicon-
Organoalkali metal compounds of the heavier alkali metals substituted alkyl derivatives of metals from groups 1, 2,
with more highly substituted alkyl groups can be formed from and 3 have been recently reviewed.17 A diverse range
the reaction of an alkane with the appropriate methyl derivative of structures has been discovered with the alkali metals.
(MMe; M = Na,19 K,20 Rb,21 and Cs21 ) (equation 18). More recently, some additional structures and an important
discussion of structural trends observed among the silicon-
RH + MMe RM + MeH(R = C(SiMe3 )3 ) (18) substituted alkyl derivatives of the alkali metals have also
been published.34 Tris(trimethylsilyl)methyl lithium forms
Alkylalkali metal compounds are also commonly formed a solvent-free dimer, as well as several ate complexes
from reactions with organomercury compounds. Solvent- in the presence of bases (THF or TMEDA). In the alkyl-
free LiC(SiMe3 )3 has been prepared by the reaction of bridged dimer of tris(trimethylsilyl)methyl lithium (2), there
an organomercuryhalide with butyl lithium in hexanes are interactions between the CH bonds of the silyl ligand
(equation 19).17 and the lithium atoms (3) (Li to C distances of 254.1(7) and
246.6(6) pm).17
2BuLi + BrHgR LiR + LiBr + HgBu2 (R = C(SiMe3 )3 ) (19)
SiMe3
Me3Si
3.1.2 Structures SiMe3 Si
C C C
In solutions, the extent of the oligomerization or the degree Li Li Li Li
of association of alkylalkali metal compounds is dependent
C C C
on several factors: the size of the metal, the steric bulk of
the alkyl substituent, the concentration of the compound, the Me3Si SiMe3 Si
identity of the solvent, the presence of additional bases, and SiMe3
the temperature of the solution. More information is available
(2) (3)
on the structures of organolithium compounds than the heavier
alkali metal compounds since they are widely used as reagents
in organic synthesis and because of the availability of 6 Li Silicon-substituted alkyl derivatives of the heavier alkali
NMR data. metals are increasingly being used in the synthesis of
In the solid state22,23 and in the gas phase,2426 methyl other organometallic compounds because of their solubility.
lithium exists as a tetramer. The tetramer of methyllithium in Perhaps, it is this enhanced solubility that has allowed for
the solid state can be viewed as a distorted cube of carbon and the structural characterization of many of these compounds
lithium atoms (LiC, 2.36 A; Li Li, 2.68 A) (1). in recent years. Tris(trimethylsilyl)methyl potassium and
rubidium both crystallize as solvent-free compounds from
ether solution. The potassium derivative consists of infinite,
H3C Li linear chains of alternating potassium cations and alkyl
Li CH3 anions (average KC = 309.7(11) pm).17,20 There are weak
interactions between the chains, potassium to six methyl
Li CH3 groups (three on each side), allowing the potassium to be
eight-coordinate (K C range from 318.7 to 331.1 pm).17,20
H3C Li The solvent-free bis(trimethylsilyl)methyl sodium and
bis(trimethylsilyl)methyl lithium are isostructural and cry-
(1)
stallize as polymeric chains of alternating cations and
anions.35,36 The potassium compound also crystallizes
Structurally similar tetramers are maintained in solutions as an infinite polymer chain of alternating cations and
with electronic donors (THF or TMEDA).27,28 For example, anions with one thf molecule on each potassium cation.37
the same core structure exists for the methyllithium TMEDA Bis(trimethylsilyl)methyl cesium crystallizes as a polymeric
adduct. Ab initio methods have been used to study the chain with one TMEDA ligand coordinated to each cesium
aggregation of various methyl lithium oligomers in the cation.38 The PMDTA adduct of the rubidium derivative (4)
presence of various donor ligands.29 The heavier alkali crystallizes as an alkyl-bridged dimer (Rb C Rb, 104.7(2);
metal (M = K, Rb, Cs) methyl compounds have more ionic Rb C, 336.1(10), 348.5(8)) with terminal PMDTA ligands.37
ALKALI METALS: ORGANOMETALLIC CHEMISTRY 5
3.2.1 Synthesis
OMe Me2Si
OMe For synthetic application, the formation of substituted
Me2Si
Li C alkenylalkali metal compounds with high regio- and
C Li stereoselectivity is desirable. Alkenyl halides react with
MeO SiMe2 organolithium reagents by metal-halide exchange to give
Li Me3Si C alkenyllithium compounds. The halides of choice include
SiMe3
Me2Si Me3Si bromide and iodide; alkenyl chlorides favor -hydrogen
OMe
C Li metallation. Low-reaction temperatures permit retention
SiMe3 of the stereochemistry of the original alkenyl halide
Me3Si
in the alkenyllithium product (equation 21). Vinylsodium
Li C
SiMe3 and potassium can be prepared from direct reaction
MeO SiMe2 of the metals with vinyl bromide or vinyl chloride
Me3Si
C SiMe3 Li respectively.
Me2Si OMe
Li C
C Li THF/Et2 O/C5 H12
(E)-RHC=CHBr + 2t-BuLi
MeO SiMe2 120 C
SiMe2 MeO (E)-RHC=CHLi + t-BuH + Me2 C=CH2 (21)
(5)
Alkenyllithium compounds can also be prepared by
Ph2
Ph2 metallation of alkenes, particularly when alkenyl hydro-
P gens are rendered acidic by an -substituent (equation 22).
P
Li Transmetallation of alkenyl stannanes with organolithium
PPh2
reagents gives alkenyllithium compounds with retention of
alkene stereochemistry (equation 23). Tin lithium transmet-
Me2Si
SiMe2 allation has been used to prepare 1,4-dilithio-1,3-butadiene.43
Si Monosubstituted alkenyllithium compounds RHC=CHLi,
Me2
can also be prepared from the corresponding diorganotel-
(6) luride, RHC=CHTeBu, by reaction with butyllithium in
6 ALKALI METALS: ORGANOMETALLIC CHEMISTRY
THF.44 M
C C M C C M
RHC=C(SO2 Ph)H + MeLi RHC=C(Li)(SO2 Ph) (22)
M
low temp.
(E)-Me3 SiHC=CHSnR3 + BuLi (7) (8)
(E)-Me3 SiHC=CHLi (23)
Ph
R
3.2.2 Structures and Reactivity C
C
M M C
Vinyllithium is tetrameric in THF solution. Alkenyllithium C tmpda Li
compounds containing -hydrogen or alkyl substituents C C Li tmpda
do not isomerize readily; however, the presence of M C
donor solvents promotes (Z)-to-(E) isomerization. Those C C
compounds containing -aryl substituents isomerize readily. C
R R
The configurational stabilities of HDC=C(Li)X, where X is
Ph
CN or CO2 Me, and RHC=C(Li)Y, where Y is OR or Me3 Si,
have been investigated.45,46 (9) (10)
Lithio-enynes of the type (Z)-RHC=C(Li)CCHR are
configurationally stable at temperatures below 120 C,
and the lithio-diene, (Z,Z)-BuHC=C(Li)CHC=CHBu, is studies suggest that these interactions are weak in alkali metal
configurationally stable at temperatures below 78 C.47 acetylide compounds (only 0.73 kcal mol1 for LiCCR),
X-ray structural determinations of alkenylalkali metal and the strength apparently decreases with increasing size
compounds are particularly sparse. (0.07 kcal mol1 for Cs).53
3.3.1 Synthesis
3.4.1 Synthesis
The high acidity of the CH bonds in acetylene compounds
allows for the synthesis of alkali metal acetylene compounds Orthometallation of substituted arenes has been re-
by direct reaction with the metals. viewed.54,55 The ortho-directing ability of substituents in
(6 -arene)Cr(CO)3 complexes decreases as F > CONHR >
NHCOR > CH2 NR2 OMe CH2 OMe.56 Heavier alkali
3.3.2 Structures metal arenes can be formed from the reaction of phenyl
lithium with sodium or potassium alkoxides.
The heavier alkali metal compounds of the formula
MCCCH3 (M = Na, K, Rb, Cs) have been studied by
X-ray powder diffraction and are found to be isostructural, 3.4.2 Structures and Reactivity
crystallizing with a tetragonal unit cells.4851 The heavier alkali
metals prefer a double -bridged structure (7) rather than a The degree of oligomerization of various aryllithium
linear -bonding structure (8). The metal carbon distances compounds in the presence of donor species has been
are similar for both carbon atoms in the acetylides, MCCH determined by NMR (13 C and 7 Li).57,58 X-ray struc-
and MCCCH3 . The polymer-sheet structure (9) has tures of [PhLiOEt2 ]4 (11),59 [PhLiTMEDA]2 (12),60 and
increasing symmetry in -bonding between layers with PhLiPMDTA (13)61 illustrate the diversity of structures of
an increase in the size of the metal. Lithium acetylides aryllithium compounds containing donor ligands. Recently,
typically crystallize with more linear structures. For example, the utility of aryllithium compounds in aryl aryl coupling has
the single-crystal X-ray structure of [(PhCCLi)tmpda]2 been demonstrated to produce a range of unusual substituted
shows a preference for end-on bonding rather than side-on biaryls.62
bonding (10).52 The solvent-free phenyl derivatives of the heavier alkali
The differences in bonding preferences in lithium acetylides metals have not been structurally characterized. Phenyl
may be confused by the competition from coordinating sodium dimers crystallize in the presence of donors such as,
solvents. In the absence of solvent interactions, as in PMDTA and TMEDA.18 Using the bulky mesityl-substituted
the crystal structure of LiCCSiMe2 C6 H4 OMe, nearly derivatives, a solvent-free arylsodium compound has been
symmetric -interactions are observed.53 Computational characterized [Na(C6 H3 Mes2 -2,6)]2 .63
ALKALI METALS: ORGANOMETALLIC CHEMISTRY 7
CN CN
Ph Li(OEt2) Li+
Ph
Ph Ph Ph (27)
Li(OEt2) Ph N
N H H
Li Li H H
N N Li+
Li(OEt2) Ph
Ph Li(OEt2)
4.1.1 Synthesis
Allylalkali metal compounds exhibit dynamic isomer-
The direct reaction of allyl halides and alkali metals izations and bond rotations in solution. In THF solution,
leads to extensive coupling of the allyl fragments, so allylalkali metal complexes undergo CC bond rotations with
other synthetic routes must be used for the preparation of activation energies normally in the range of 45 75 kJ mol1 .
allylalkali metal compounds. The metallation of appropriate 1-Alkylallylalkali metal compounds usually exist as a dynamic
alkenes is an effective route to allyl compounds. A wide mixture of (E) and (Z) isomers (15), with a thermodynamic
variety of metalating agents have been used, including preference for the (Z) configuration. The rates of isomeriza-
tion of trans-neopentylallyl metal complexes in THF solution
lithium amides, alkyllithium reagents, Me3 SiCH2 K, and
decreases in the sequence Li > Na > K.67 Numerous stud-
Me2 SiCH2 Cs. Transmetallation of allylstannanes or -mercury
ies of the structures and dynamic properties of allyllithium
compounds gives convenient routes to halide-free allylalkali
compounds have been reported.6872
metal compounds (equations 24 26).64 The thermal ring-
opening of the cyclopropylithium species can also be used
to prepare allyllithium complexes (equation 27). 4.2 Pentadienylalkali Metal Compounds
the Cp ring to the metal ion, although ion pair structures 7 RELATED ARTICLES
having uncoordinated substituted Cp anions are observed with
chelating donors, such as polyethers or crown ethers. Alkali Metals: Inorganic Chemistry; Alkaline Earth
Metals: Organometallic Chemistry; Beryllium & Magnesium:
Organometallic Chemistry; Periodic Table: Trends in the
Properties of the Elements.
6 HYDROCARBON RADICAL ANION
AND DIANION COMPOUNDS
8 FURTHER READING
6.1 Synthesis and Reactivity
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form paramagnetic radical anions or diamagnetic dianions.
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46. R. Knorr and T. von Roman, Angew. Chem., Int. Ed. Engl., 75. G. Fraenkel, J. H. Duncan, K. Martin, and J. Wang, J. Am.
1984, 23, 366. Chem. Soc., 1999, 121, 10538.
ALKALI METALS: ORGANOMETALLIC CHEMISTRY 11
76. S. Schade and G. Boche, J. Organomet. Chem., 1998, 550, 381. 86. N. L. Holy, Chem. Rev., 1974, 74, 243.
77. M. J. Kaufmann, S. Gronert, and A. Streitwieser Jr, J. Am. 87. M. Szwarc, Acc. Chem. Res., 1972, 5, 169.
Chem. Soc., 1988, 110, 2829. 88. G. R. Stevenson, M. K. Ballard, and R. C. Reiter, J. Org.
78. S. Gronert and A. Streitwieser Jr, J. Am Chem. Soc., 1988, 110, Chem., 1991, 56, 4070.
2836. 89. A. Sekiguchi, K. Ebata, C. Kabuto, and H. Sakurai, J. Am.
79. S. Gronert and A. Streitwiese Jr, J. Am Chem. Soc., 1988, 110, Chem. Soc., 1991, 113, 1464.
2843. 90. A. Sekiguchi, K. Ebata, C. Kabuto, and H. Sakurai, J. Am.
80. C. Uffing, R. Koppe, and H. Schnockel, Organometallics, 1998, Chem. Soc., 1991, 113, 7081.
17, 3512. 91. J. L. Wardell, in Comprehensive Organometallic Chemistry,
81. S. Neander, U. Behrens, and F. Olbrich, J. Organomet. Chem., eds. G. Wilkinson, F. G. A. Stone, and E. W. Abel, Pergamon
2000, 604, 59. Press, Oxford, 1982, Vol. 1, Chap. 2, p. 43.
82. F. Rebiere, O. Samuel, and H. B. Kagan, Tetrahedron Lett., 92. E. Bartmann, Angew. Chem., Int. Ed. Engl., 1986, 25, 653.
1990, 31, 3121. 93. J. Barluenga, J. Florez, and M. Yus, J. Chem. Soc., Perkin
83. M. A. Edelman, P. B. Hitchcock, M. F. Lappert, D. S. Liu, and Trans. 1, 1983, 3019.
S. Tian, J. Organomet. Chem., 1998, 550, 397. 94. G. D. Stucky, Adv. Chem. Ser., 1974, 130, 56.
84. M. J. Harvey, T. P. Hanusa, and M. Pink, J. Chem. Soc., Dalton 95. N. Hu, L. Gong, Z. Jin, and W. Chen, J. Organomet. Chem.,
Trans., 2001, 1128. 1988, 352, 61.
85. S. Neander, J. Kornich, and F. Olbrich, J. Organomet. Chem.,
2002, 656, 89.
zero electrical resistance; tdfnd = 1,1,1,2,2,3,3,7,7,8,8,9,9,9-
Alkaline Earth Metals: tetradecafluorononane-4,6-dionato; tfac = 1,1,1-trifluoropen-
tmhd = 2,2,6,6-tetramethylheptane-3,5-
Inorganic Chemistry tane-2,4-dionato;
dionato; tmmhd = 2,6,6-trimethyl-2-methoxyheptane-3,5-
dionato.
William S. Rees, Jr
Georgia Institute of Technology, Atlanta, GA, USA
Glossary
LB = Lewis base; bht = 2,6-di(t-butyl)-4-methylphenoxide; 2A. As inclusion of the word metal in their title implies,
bo = 1-metalla-2,6-dioxo-3-aza-4,5-diphenylcyclohex-3- these elements are both malleable and extrudable; however,
ene; CBD = Chronic beryllium disease; dbp = 2,6-di(t- they are rather brittle. They are electrical conductors. When
butyl)phenoxide; dfhd = 1,1,1,2,2,3,3,7,7,7-decafluorohept- pure, all except the lightest, beryllium, react with atmospheric
ane-4,6-dionato; dmmhd = 2,6-dimethyl-2-methoxyheptane- O2 and/or H2 O to form a protective coating of metal oxide,
3,5-dionato; dmmod = 2,2-dimethyl-8-methoxyoctane-3,5- which acts as a surface barrier to inhibit bulk oxidation. In the
dionato; fod = 1,1,1,2,2,3,3-heptafluoro-7,7-dimethyloctane- specific case of calcium, this coating is primarily composed
4,6-dionato; Hbht = 2,6-di(t-butyl)-4-methylphenol; Hbo = of the nitride.
Benzoin -oxime; Hdbp = 2,6-di(t-butyl)phenol; Hdfhd = The inorganic chemistry of the group 2 elements can
1,1,1,2,2,3,3,7,7,7-decafluoroheptane-4,6-dione; Hdmmhd = be categorized succinctly into a rather limited focus. The
2,6-dimethyl-2-methoxyheptane-3,5-dione; Hdmmod = 2,6- overwhelming preponderance of the +2 oxidation state rules
dimethyl-8-methoxyoctane-3,5-dione; Hfod = 1,1,1,2,2,3,3- the chemistry of these elements. This ubiquitous observation,
heptafluoro-7,7-dimethyloctane-4,6-dione; Hhfac = 1,1,1,5, coupled with the severely limited energetic accessibility
5,5-hexafluoropentane-2,4-dione; Hhipa = 2-hydroxyimino- of other oxidation states, has dictated the development of
propionic acid; hipa = 2-hydroxyiminopropionate; Htdfnd = the area. These elements are comparable in much of their
1,1,1,2,2,3,3,7,7,8,8,9,9,9-tetradecafluorononane-4,6-dione; chemistry, diverging most in aspects dependent on atomic
Htfac = 1,1,1-trifluoropentane-2,4-dione; Htmhd = 2,2,6,6- size rather than electronic charge. It is in this regard
tetramethylheptane-3,5-dione; Htmmhd = 2,6,6-trimethyl-2- that the greatest diversity is displayed in these congeners.
methoxyheptane-3,5-dione; Jc = Critical current den- The span encompasses a quite broad range (Be, 111 pm;
sity of a superconducting material; n.b. = Nonbonding; Ra, 223 pm) and thereby influences some of the observed
n0 = Neutron; RE = Rare earth element; SMO = trends. This effect emerges most noticeably in the realm of
Superconducting metal oxide; Tc = Temperature of coordination chemistry.
2 ALKALINE EARTH METALS: INORGANIC CHEMISTRY
All six elements are found in Nature. Radium has no stable a controlling variable of the number of atomic orbitals
isotopes (see Isotopes & Isotope Labeling); however, 226Ra has potentially available to accommodate bonding electrons (see
a half-life of 1600 years. Its decay mode is by (4.780 MeV) Electronic Structure of Main-group Compounds). One
and emission. As a consequence of this radioactive nature consequence of its location early in the periodic table is the
(see Radioactive Decay), its chemistry remains relatively limitation on this number of orbitals to four (one s and three p),
unexplored. In several arenas, rather comprehensive studies and the concomitant delegation to be, in the primary examples,
have examined various properties of all of the lighter group four coordinate. Such restraints are removed for the other
2 elements. Efforts have been made to extend all given group 2 elements and, as we shall discover below, coordination
comparisons to radium; however, in some instances this has numbers (see Coordination Numbers & Geometries) of 6, 8,
proven rather difficult. 10, and, in certain instances, even 12, commonly are observed
One significant deviation from the influence of ionic for these elements.
chemistry for the group 2 elements is beryllium. Although
the chemistry of this lightest element of the group exhibits
indications of the presence of some covalent bonding (see
Covalent Bonds), it does not overwhelm the dominating trend 2 THE ELEMENTS
toward ionic behavior. There are several well-understood
reasons for the uniqueness of beryllium. Its comparatively The date, location, and credited scientist of discovery,
large charge/size ratio, relatively high Electronegativity and comparable information for initial pure isolation, and historical
low z nature combine to produce this observed effect. derivation of the name of each of the group 2 elements
The first of these items may be adequately explained are summarized in Table 1. The principal ore found in
by proper application of Fajans Rules. The second of Nature, the industrial preparation and purification, and
these is manifested by the comparatively small resultant the principal contemporary uses are outlined in Table 2.
electronegativity difference between Be and other atoms Several important properties of each element are listed
entering into a bonding arrangement, thus inhibiting bond in Table 3. These properties can be broken down into
polarity and promoting covalency. The final factor is the categories of general information (name, symbol,
Element Discovery Year Discoverers 1st pure isolation Isolators Named after
Beryllium 1797 Vauquelin (Paris) 1828 Wohler (Berlin) Bussy (Paris) Beryllos (Greek: beryl)
Magnesium 1755 Black (Edinburgh) 1808 Davy (London) Magnesia (Greek:
Thessaly district)
Calcium 1808 Davy (London) 1808 Davy (London) Calx (Latin: lime)
Strontium 1790 Crawford (Edinburgh) 1808 Davy (London) Strontian, Scotland
Barium 1774 Scheele 1808 Davy (London) Barys (Greek: heavy)
Radium 1898 Curie (Paris) 1910 Curie (Paris) Radius (Latin: ray)
atomic number, and relative atomic mass), chemical (radii, Table 4 Isotopes of radium
electronegativity, and reduction potential), physical (melting
point, boiling point, density, Hvap , H 0 f (gas) , electrical Mode of
Mass decay Half-life Source
resistivity, thermal conductivity, mass magnetic susceptibility,
and coefficient of linear thermal expansion), nuclear (number 213 2.7 min Th + p; Pb + C6+
of isotopes, thermal n0 cross section, and NMR (see below)), 219 103 s Daughter Th223
environmental (abundance), and electronic (first, second, and 220 0.03 s Daughter Th224
third Ionization Potential, and Electron Affinity). Several 221 30 s Daughter Th225
222 38 s Daughter Th226
excellent compilations of more exhaustive data have been 223 (AcX) 11.435 day Natural; descendant U235
assembled.112 224 (ThX) 3.64 day Natural; descendant Th232
225 14.8 day Daughter Th229
226 1622 year Natural; descendant U238
2.1 Radium 227 41.2 min Ra226 (n, )
228 (MsTh1 ) 6.7 year Natural; descendant Th232
The known inorganic chemistry of radium does not differ 229 1 min Daughter Th233
significantly from that of barium.13 The isotopes of radium are 230 1h Th + d
compiled in Table 4. The chloride, bromide, and nitrate salts of
Ra are all water soluble. For example, RaCl2 (24.5 g/100 mL
H2 O at 25 C) has a comparable solubility to BaCl2 (30.7 g).
This slight difference is the primary mode of separation of
3 NUCLEAR MAGNETIC RESONANCE
Ra from Ba. Barium sulfate frequently plays the role of a
carrier for Ra. The solubility of RaSO4 (2.1 104 g/100 mL
H2 O at 25 C) is perhaps the lowest of any of the group 2 The gaining of widespread acceptance for the great utility
elements. Other aqueous insoluble salts of Ra include CO3 2 of magnetic resonance imaging in the medical community has
and CrO4 2 . served to bring the field of NMR out of the research laboratory
Owing to the difficulty in separating Ba and Ra cleanly, and into contact with the everyday lives of many citizens.
Hahn erroneously attributed Ra radioactivity to Ba and thereby Although the most widely exploited nuclei remain 1 H, 13 C, and
31
passed over the discovery of nuclear fission (see Binding P, the inorganic chemist has available a much wider variety
Energy of Nuclei). His sample of BaSO4 was not the pure of potential choices. Each of the group 2 elements, except Ra,
Ba compound, and the unknown Ra contaminant led to his has an isotope that possesses the requisite properties for NMR
observation and incorrect conclusion. observation. These are presented in Table 5, together with
4 ALKALINE EARTH METALS: INORGANIC CHEMISTRY
Table 5 Nuclear magnetic resonance Additionally, Ca2+ plays a role in the clotting of blood
9 25 43 87 137 13
and the mechanism of muscle contraction that maintains
Nuclide Be Mg Ca Sr Ba C
a consistent heart rhythm (see Calcium-binding Proteins).16
Abundance 100 10.00 0.135 7.00 11.23 1.10 The composition of green plant Chlorophyll is centered around
(%) Mg2+ . This nitrogen-based macrocyclic ligand-containing
Nuclear spin 3/2 5/2 7/2 9/2 3/2 1/2 molecule is a derivative of the tetrapyrrole porphine, a
Frequency 14.053 6.1195 6.728 4.333 11.113 25.144
Sensitivity 13.9 2.67 6.40 2.69 0.776 15.9 highly conjugated heterocyclic tetradentate alkaloid. During
(103 ) plant photosynthesis, it is this ligand that participates in
Receptivity 78.8 1.54 0.0527 1.07 4.41 1.00 one-electron redox reactions, not the metal. The apparent
Quadrupole 0.052 0.22 0.05 0.36 0.28 0 function of the Mg2+ is predominantly structural in origin.
moment The two-dimensional rigidity imparted to the ring system
(1028 )
reduces thermal vibration energy loss, and thus increases the
percent conversion. Additionally, the role of a five-coordinate
species formed by the inclusion of hydrogen bonds from
comparative data for 13 C. This will allow the reader to place water is integral in the stacking of units into the three-
these rather esoteric nuclei in their proper perspective with dimensional antenna arrays required for absorption of light
respect to a commonly employed organic analytical technique. (680 700 nm).17 Although, in principle, any nonredox-active
It is noteworthy that all of the group 2 elements except for 43 Ca metal of the proper ionic radius could fulfill this role, in
have a higher receptivity than 13 C, several of them significantly Nature only Mg2+ has been observed to perform this seminal
(137 Ba > 4) and one of them overwhelmingly (9 Be > 78) contribution to the biological systems.
larger than the corresponding relative assignment of 13 C The total mass per element in a human of average mass
1.00. In all probability, the development of techniques based (70 kg), the oral toxic intake, and the daily dietary intake
on these nuclei have been hampered, to date, by the high for the group 2 elements are summarized in Table 6. These
odd-halves (>1/2) spin associated with all of the nuclides numbers reflect the total concentrations of the elements in all
of interest. This impedance may be diminished, however, by forms; however, it is primarily as the divalent Cation that they
the recent elegant work employing a double rotating solid- are found. In this capacity, they also serve an essential function
state probe for NMR that reduces the quadrupole moment by their contribution to specific ionic equilibria in living cells.
contribution to line-broadening.14 The applicability of this Both calcium and magnesium have been classified as essential
technique to mineralogy, geology, and catalyst identification bulk elements, falling into the subcategory of macrominerals.
should be widespread. Although one report claims that omission of either strontium
or barium from the diet of rats and guinea pigs resulted
in depressed growth and reduced calcification of bones and
teeth, this hint at the essential role of the heavier group 2
4 BIOLOGICAL ROLES elements has neither been confirmed nor rejected in the past
four decades.15 It is relatively well understood that both Sr and
In a comparable manner to the discrimination found for Ba show some stimulatory action, are relatively nontoxic (see
the group 1 elements ([Na+ ] is higher outside cells and Table 6 for Ba), and will mimic (spare) Ca in most biological
[K+ ] is higher inside cells) the observation is that [Mg2+ ] systems. To date, no essential or stimulatory function has been
found for Be.18 The obvious toxicity due to the radioactive
is higher inside animal cells and [Ca2+ ] is higher in the
nature of Ra is discussed elsewhere.
body fluids outside the cells.15 Complexes between ATP
and Mg2+ are one component of phosphohydrolase and
phosphotransferase enzymes (see Enzyme) involved in the 4.1 Beryllium Biochemistry
release of energy from ATP. In animals, the utilization of
Mg2+ plays a major role in nerve fiber impulse transmission. There has been much confusion about the toxicity of Be.19
In animal teeth (enamel (fluoroapatite, [3{Ca3 (PO4 )2 }CaF2 ])) Numerous reports are based on incomplete research and, in
and bones (apatite, Ca3 (PO4 )2 ), the key contribution of Ca2+ a limited number of instances, have been misquoted at great
to the structural formation of biological systems is manifested. length in the subsequent scientific literature. For example,
Be Mg Ca Sr Ba Ra
one authoritative work states It should be noted that not Table 7 Ionic radius (pm)
more than 500 g Be total, in any chemical form, should be
kept in a laboratory; otherwise, in the event of fire, beryllium Elementa
Coordination
compounds could be vaporized or blown about to such an number Be Mg Ca Sr Ba Ra
extent as to constitute a hazard to the surrounding area.7
Yet, in 1948, after a major fire and explosion in a Lorain, 4 27 57
6 45 72 100 118 135
Ohio, beryllium manufacturing facility, which included the 8 112 126 142 148
ignition of some 2.5 tons of Mg in the BeO processing factory, 12 170
no firefighters, police, naval reserve personnel (activated for
a
crowd control), or spectators reported any evidence of the All ions have 2+ charge and [group 18] electron shell configuration.
symptoms of beryllium diseases.19
With the data available at this point, it does not appear
that ingestion of beryllium compounds presents a significant
health hazard. Likewise, there is no evidence to indicate that
simple skin contact with elemental beryllium or its compounds the elements differ, as expected, from 4 (for Be) to 12
will result in dermatoses. The unequivocal establishment of (for Ba) (see Coordination & Organometallic Chemistry:
an immunological basis for Chronic beryllium disease (CBD) Principles).3 On the whole, all observed geometries are
located this disorder to be a pulmonary granulomatous process. standard (see Coordination Numbers & Geometries). The
CBD is a localized response to an insoluble and persistent absolute solubilities of typical salts have been summarized
irritant. Acute pulmonary beryllium disease is caused by (Table 8).7 The gas-phase bond dissociation energies trail
airborne particulates of soluble beryllium salts, primarily the pattern forecast by examination of electronegativity
BeSO4 or BeF2 . This disease is generally limited to the upper and orbital overlap differences (Table 9).8 A wide array of
respiratory tract. Although there were 30 60 new cases per typical reactions could be found for the group 2 elements; a
year during the period 1942 1947, there have been less than 10 minor sampling of this diverse chemistry is presented here
total confirmed cases within the past 40 years. In almost each (Table 10).12
instance, it was a single isolated case resulting from accidental
exposure during maintenance work at a manufacturing facility.
Thus, although perhaps not as benign as its heavier congeners
Mg and Ca, the relative risk posed by Be is rather small. When
compared with other inorganic compounds, such as AsH3 , the Table 9 Strengths of bonds in diatomic molecules of the alkaline
exposure limits of 25 g m3 per 30 min place this threat in earth metals with halogens (kcal mol1 )
perspective.
Be Mg Ca Sr Ba
F 151 123 132 132 138
4.2 Coordination Chemistry Cl 110 97 103 112 114
Br 89 81 96 97 102
The ionic radii (Table 7) of the group 2 elements I 69 63 78 80 86
follow the predicted trends.6 The coordination numbers of
Table 8 The solubilities of the salts of the alkaline earth metals in water at 25 C and 100 C (g/100 g solution)a
Mg Ca Sr Ba Ra
Reaction Comment
M + 2H2 O M(OH)2 + H2 Be probably reacts with steam; Mg with hot water, and Ca, Sr, and Ba react rapidly
with cold water
M + 2HX MX2 + H2 All the metals react with acids, liberating hydrogen
Be + NaOH Na2 [Be(OH)4 ] + H2 Be is amphoteric
2M + O2 2MO Normal oxide formed by all group members with excess oxygen
Ba + O2 BaO2 Ba also forms the peroxide
M + H2 MH2 Ionic saltlike hydrides formed at high temperatures by Ca, Sr, and Ba
3M + N2 M 3 N2 All the metals form nitrides at high temperatures
3M + 2P M3 P2 All the metals form phosphides at high temperatures
M+S MS All the metals form sulfides
M + Se MSe All the metals form selenides
M + Te MTe All the metals form tellurides
M + F2 MF2 All the metals form fluorides
M + Cl2 MCl2 All the metals form chlorides
M + Br2 MBr2 All the metals form bromides
M + I2 MI2 All the metals form iodides
M + 2NH3 M(NH2 )2 + H2 All the metals form amides at high temperatures
5 COMPOUNDS OF GROUP 2 ELEMENTS WITH the evolution of H2 (equation 8). This specific property has
HYDROGEN led to wide employment of the compounds as agents for
removal of water and other protic impurities from large
The group 2 elements Mg, Ca, Sr, and Ba all react with volumes of organic liquids as one predistillation purification
H2 (g) to form Hydrides of the formula MH2 (e.g. equation 1). technique.
The dihydride of beryllium is difficult to prepare and less
CaH2 + 2H2 O Ca(OH)2 + 2H2 (g) (8)
thermodynamically stable than the dihydrides of the heavier
group 2 congeners. Impure BeH2 (contaminated with various
amounts of diethyl ether) was made historically by reducing The heavier group 2 dihydrides (CaH2 , SrH2 , and BaH2 )
BeCl2 with lithium aluminum hydride (LiAlH4 ) (equation 2). are ionic (see Ionic Bonds, Ionic Character), containing the
Pure samples can be obtained by reducing BeCl2 with lithium hydride ion (H ). Beryllium and magnesium dihydrides are
borohydride (LiBH4 ) to give BeB2 H8 (equation 3), then covalent and polymeric (see Polymer). (BeH2 )n presents an
heating BeB2 H8 in a sealed tube with triphenylphosphine interesting structural challenge. In the gas phase, it seems
(PPh3 ) (equation 4). Alternatively, it may be prepared by probable that several species may be present, comprising
a thermal -Hydride Elimination of isobutene from bis(t- polymeric chains and rings. The solid state is polymeric, and
Bu)beryllium at temperatures of 100 C (equation 5).20 the single-crystal X-ray diffraction structure indicates that it
Additionally, convenient methods for the preparation of MgH2 consists of chains of beryllium atoms containing hydrogen
bridges between them (Figure 1).
are reduction of Mg(anthracene) (equation 6) and exchange
Each Be atom is connected to four H atoms, and each
between alkyl magnesium compounds and phenylsilyl
H atom is connected to two Be atoms. Since Be has
hydrides (equation 7).21
two valence electrons, and H only one, obviously there
are insufficient electrons to fulfill the traditional organic
Ca(s) + H2 (g) CaH2 (s) (1)
two-center, two-electron bonding description. Alternatively,
2BeCl2 + LiAlH4 2BeH2 + LiCl + AlCl3 (2) three-center interactions persist, whereby banana-shaped
BeCl2 + 2LiBH4 BeB2 H8 + 2LiCl (3) molecular orbitals (a three-center, two-electron bond, see
Three-center Bond) connect the BeHBe atoms, each
BeB2 H8 + 2PPh3 BeH2 + 2Ph3 PBH3 (4) containing two electrons (see Figure 2 for the molecular orbital
100 C scheme (see Molecular Orbitals) for this type of Delocalized
Be(t-Bu)2 BeH2 + 2H2 C=CMe2 (5)
H2
Mg(anthracene) MgH2 (6) H H H
MgBu2 + 2Ph3 SiH MgH2 + 2Ph3 SiBu (7) Be Be Be
H H H
n
All the metal hydrides are reducing agents and readily are
decomposed by water, dilute acids, alcohols, thiols, primary Figure 1 Polymeric structure of BeH2 , containing three-center,
and secondary amines, and other protic compounds, with two-electron BeHBe bridging bonds
ALKALINE EARTH METALS: INORGANIC CHEMISTRY 7
to the tremendous stability of the N2 molecule, a large a single THF ligand at each metal center without gross
amount of energy is required to convert one dinitrogen structural change (i.e. [Ba{N(SiMe3 )2 }2 (THF)]2 ). Addition of
molecule with a triple bond into two N3 (nitride ions). The a second molecule of neutral THF, however, provides enough
large amount of energy required comes from the substantial steric bulk to ensure that the Ba{N(SiMe3 )2 }2 (THF)2 adduct
quantity of Lattice Energy released upon formation of the crystallizes as a monomer. Remarkably, isostructural dimers of
crystalline solid. The lattice energy is particularly high the form [M{N(SiMe3 )2 }2 ]2 exist for all the metals Mg to Ba.
as a consequence of the high charges on the ions (M2+ Even though the metal radii in these compounds vary by more
and N3 ). This prevalence of group 2 elements to form than a factor of two (Table 7), the bis(trimethylsilyl)amido
nitrides contrasts with the group 1 elements, where Li3 N ligands adapt to the range of metal ligand distances without
is the only nitride reported. The very small size of Li+ , requiring changes in nuclearity.
resulting in a high lattice energy, explains this observation.
These thermodynamic values may be calculated using a
Born Haber Cycle. Be3 N2 is rather volatile, in accord with
the greater tendency of Be to covalency, but the other 8 HYDROXIDES, CARBONATES, BICARBONATES,
nitrides are involatile. All the nitrides are crystalline solids OXIDES, AND PEROXIDES OF GROUP 2
that decompose on heating and react with water, liberating ELEMENTS
ammonia and forming either the metal oxide or hydroxide,
(e.g. equation 16). The elementary forms, hydroxides, carbonates, bicarbon-
ates, oxides, and peroxides of the group 2 elements all are
3Ca(s) + N2 (g) Ca3 N2 (s) (15) highly interrelated (equations 17 24) and hence are discussed
Ca3 N2 + 6H2 O 3Ca(OH)2 + 2NH3 (16) together (see Oxides: Solid-state Chemistry and Chalco-
genides: Solid-state Chemistry).12
Central metal
Compound coordination number Nuclearity Average MN distance (A) Methoda
Be[N(SiMe3 )2 ]2 2 Monomeric 1.566 (17) E27
[Mg{N(SiMe3 )2 }2 ]2 3 Dimeric 1.975 (5) t-N X28
2.151 (6) -N
Mg[N(SiMe3 )2 ]2 (THF)2 4 Monomeric 2.021 (7) X29
[Ca{N(SiMe3 )2 }2 ]2 3 Dimeric 2.275 (9) t-N X30
2.47 (1) -N
Ca[N(SiMe3 )2 ]2 (DME) 4 Monomeric 2.271 (3) X30
[Sr{N(SiMe3 )2 }2 ]2 3 Dimeric 2.43 (2) t-N X31
2.63 (2) -N
Sr[N(SiMe3 )2 ]2 (DME)2 4 Monomeric 2.538 (7) X31
[Sr{N(SiMe3 )2 }2 (dioxane)]n 4 1-D polymer 2.449 (7) X32
[Ba{N(SiMe3 )2 }2 ]2 3 Dimeric 2.576 (3) t-N X25
2.798 (3), 2.846 (4) -N
[Ba{N(SiMe3 )2 }2 (THF)]2 4 Dimeric 2.602 (9) t-N X25
2.834 (9), 2.903 (10) -N
Ba[N(SiMe3 )2 ]2 (THF)2 4 Monomeric 2.592 (8) X25
a
E = gas-phase electron diffraction; X = single-crystal X-ray diffraction; t = terminal; = bridging.
ALKALINE EARTH METALS: INORGANIC CHEMISTRY 9
Be(OH)2 is amphoteric, but the hydroxides of Mg, Ca, Table 12 Desirable properties for
Sr, and Ba are basic. The basicity increases from Mg to furnace liners
Ba, and group 2 elements portray the usual trend that
1. High melting points (>2500 C)
basic properties increase on descending a group. Solutions 2. Low vapor pressures
of Ca(OH)2 , called lime water, are used to detect carbon 3. High thermal conductivities
dioxide. When CO2 (g) is bubbled through these solutions, 4. Low chemical reactivities
they become opaque (milky), owing to the formation 5. Low electrical conductivities
of a suspension of CaCO3 . If additional CO2 is passed
through these cloudy solutions, the turbidity dissipates and
soluble calcium bicarbonate is formed from the excess CO2 Mg + H2 O MgO + H2 (g) (28)
(equation 25).
All the elements in group 2 burn in O2 (g) to form oxides
excess (MO). Metallic Be is relatively unreactive in the bulk form,
CO2
Ca(OH)2 (aq) + CO2 (g) CaCO3 ( ) + H2 O(l) and does not combust below 600 C, but the powder, as a
Ca(HCO3 )2 (aq) (25) result of the higher surface area, is significantly more reactive
and burns brilliantly. The elements also burn in air, forming a
The bicarbonates of group 2 elements are stable only mixture of oxide and nitride. Mg burns with dazzling brilliance
in solution. An interesting and aesthetically pleasing in air, evolving substantial amounts of heat (equation 29). This
consequence of this in Nature greets spelunkers (cavers) to is used to start the Thermite Reaction between iron oxide and
sights of cavern columns. Underground caves, which occur aluminum, and also to provide light in flash photography using
predominately in regions of the planet heavily concentrated light bulbs, not electronics.
with limestone deposits and which are rather somewhat more
Mg + air MgO + Mg3 N2 (29)
arid today than in historical times, often have stalactites
growing down from the roof, and stalagmites growing up from
the floor. Water percolating through the limestone contains Beryllium oxide usually is prepared by ignition of the
some Ca(HCO3 )2 in solution. The soluble bicarbonate slowly metal, but the other metal oxides are predominately obtained
decomposes into the insoluble carbonate, thus resulting in the by thermal decomposition of the carbonates (MCO3 ). Other
slow growth of the stalactites and stalagmites. The observation oxosalts, such as M(NO3 )2 and MSO4 , and also M(OH)2 ,
of a wide array of colors in these natural structures eminates all decompose to the oxide on heating. The oxosalts are less
from trace concentrations of elements of the d-block metals of stable to heat than the corresponding group 1 salts because
the periodic table. These transition elements possess electrons the metals and their hydroxides are less basic than those of
that undergo optical transitions between orbitals in the visible group 2.
region of the electromagnetic spectrum, thereby treating the Magnesium oxide is not very reactive, especially if it has
observer to a wonder of the world (Carlsbad Caverns in New been ignited at high temperatures, and for this reason it is
Mexico, USA).33 used as a refractory. BeO also is used as a refractory. They
The heavier group 2 elements (Ca, Sr, Ba) have oxidation combine a number of properties that make them useful for
potentials similar to those of the corresponding group 1 metals, lining furnaces. These factors are summarized in Table 12.
and are rather high in the electrochemical series. They react Calcium oxide, SrO, and BaO react exothermically with
with cold water quite readily, liberating hydrogen and forming water, forming hydroxides (e.g. equation 30). Magnesium
metal hydroxides (e.g. equation 26) (Table 10). The reduction hydroxide is extremely insoluble in water (1 104 g L1 at
potential of beryllium is much less than those for the rest of 20 C) but the other hydroxides are soluble and the solubility
the group (Table 3). This indicates that beryllium is much less increases as one progresses down the group: Ca(OH)2
electropositive (less metallic) than the others, and beryllium 2 g L1 ; Sr(OH)2 8 g L1 ; Ba(OH)2 39 g L1 . Beryllium
does not react with water. There is some doubt whether it reacts hydroxide is soluble in solutions containing an excess of OH ,
with steam to form the oxide (BeO), or fails to react at all and therefore is amphoteric (see Amphoterism). Magnesium
(Table 10). Magnesium has an intermediate reduction value, hydroxide is weakly basic, and is widely used to treat acid
and although it does not react with cold water, it decomposes indigestion in human stomachs. The other group 2 element
in hot water (equations 27 and 28). Magnesium forms a hydroxides are strong bases.
protective layer of oxide, so, despite its favorable reduction
potential, it does not react readily unless the oxide layer is CaO + H2 O Ca(OH)2 (30)
removed by amalgamation with mercury. In the formation of
the oxide film, it resembles the group 13 element aluminum. Beryllium oxide is covalent and has a zinc blende (wurtzite)
structure, but all the others are ionic and have a rock salt
Ca + 2H2 O Ca(OH)2 + H2 (g) (26) structure (Figure 3).23 Attempts to predict the structures (using
Mg + 2H2 O Mg(OH)2 + H2 (g) (27) the ionic sizes and the radius ratio) only are partly successful.
10 ALKALINE EARTH METALS: INORGANIC CHEMISTRY
s
E n.b.
n.b.
Be sp3 F sp3
sb
Stabilityd
vaporization rate of Ba(tmhd)2 so that its vapor pres- used as the carrier gas, instead of an oxygen donor.72 It has
sure remains constant for several hours.57 This effect was been reported that addition of a nitrogen-containing base to
previously observed by Fujinaga et al. while trying to sep- the carrier gas causes the barium source to melt between 70
arate -diketonate compounds by gas chromatography.5861 and 100 C and to become volatile between 130 and 230 C
Although decomposition of Ba(tmhd)2 is reduced by the (1 atm), without any visible decomposition, depending on the
addition of excess neutral -diketone, high temperatures amine used. One difference between the nitrogen and oxygen
(280 300 C) are still required to volatilize the precursor. donor ligands is that, while stable, isolable complexes were
The first report of enhanced volatility of a barium obtained between the oxygen donor ligands and barium bis(-
source compound was made by Spee, Mackor, and diketonate) complexes, no such species were initially reported
coworkers, who noted that thermally stable complexes can for amines or ammonia. Nitrogen-free films of barium oxides
be synthesized using Ba(hfac)2 and a neutral coordinating have been deposited at 500 C under ambient pressure, with
donor ligand such as a polyether, MeO(CH2 CH2 O)n Me (n = NEt3 vapor added to the nitrogen/oxygen carrier gas, while
1 4) (Figure 9).6266 These complexes show an increased for the barium precursor, Ba(tmhd)2 , the temperature was
volatility at reduced pressures relative to their uncomplexed maintained at 130 C.73
parent compounds. The best results were obtained with Subsequent to the initial report of enhanced vapor transport
Ba(hfac)2 [MeO(CH2 CH2 O)4 Me], which becomes volatile at of [Ba(tmhd)2 ]x by addition of NH3 to the carrier gas, it
150 C at 0.03 Torr. Despite the increased volatility of the was discovered that an isolable compound is formed between
barium source, the films deposited still contain significant these two species (equation 40). The X-ray diffraction crystal
quantities of BaF2 , and there has been no report that the structure of [Ba(tmhd)2 (NH3 )2 ]2 indicated it to be a highly
nonfluorinated Ba(tmhd)2 can be volatilized by this method. symmetric dimer (Figure 10). The localized geometry around
This approach has been expanded by others.67,68 Although the eight-coordinate barium atoms is nearly perfectly square-
demonstrative of the desire of barium to achieve coordination antiprismatic. The coordinated ammonia is not retained upon
numbers of 8 12, this new chemistry has not led, at this point, vapor transport. Thus, in all probability, it is the primary
to a reported volatilization of fluorine-free barium compounds. purpose of the added NH3 (g) to break up [Ba(tmhd)2 ]x
Other workers have added THF or H2 O to the carrier gas from the solid and transport it as [Ba(tmhd)2 (NH3 )2 ]2 , or
stream in efforts to affect the requisite vapor pressure increase some other comparably lowered nuclearity species, in the
in Ba(-diketonate)2 compounds.6971 The objective of all vapor phase.
these experiments was to coordinatively saturate the barium
atom in the vapor phase by incorporation of the lone pair +NH3
electrons on the oxygen atoms of the neutral ligands into the [Ba(tmhd)2 ]n [Ba(tmhd)2 (NH3 )2 ]2 (40)
NH3
bonding sphere of the metal. At the temperatures demanded
for vapor transport, the equilibrium for dissociation of these Several additional examples of intermolecular stabilization
ligands is rather unfavorable; therefore, any anticipated gain have been reported. Pez74 has prepared Ba(hfac)2 (18-
will be minimal. crown-6) and Gleizes75 has obtained the structure of
A more dramatic change in volatility and stability of Ba(tmhd)2 (MeOH)2 . The isolation of Ba(tmhd)2 (TMEDA)2
barium bis(-diketonate) complexes is seen when a nitrogen- (Figure 11) has been achieved as well, although the vapor-
containing base, such as an amine or ammonia, is added to or phase composition of this species was not determined.76
F(1)
F(8)
F(3) F(7)
F(2) F(9)
O(6) O(8)
O(5)
O(1)
N(1) O(4)
Ba(1)
F(4)
F(10) O(1) Ba(1)
O(7) O(4) O(9)
F(6) F(11) O(2)
O(2) O(3)
F(5)
O(3) F(12) N(2)
+ MeO2C OMe
O O
O(2)
OMe + MeOH
N(15) (41)
O O
MeO
t-Bu
(9)
Figure 11 The molecular structure of Ba(tmhd)2 (tmeda)2
a known four-coordinate square-planar complex.2 Thus, at workers. However, it is important to realize that the use of
this time, the observation of the presence of a rather weak fluorinated -diketonates (see above) has always been found
fifth oxygen atom interaction with each copper center in the to result in the primary deposition of BaF2 , and that this
solid state may be explained as being the consequence of material is then subsequently converted in a second reaction
molecular packing, and not strongly dominated by tightly step (hydrolysis) to the sought-after metal oxide. BaX2 (18-
bound intermolecular interactions. crown-6) type compounds also have been reported (X = Cl,
Br, I, NO3 , OH, SCN) (see Macrocyclic Ligands).83
2KOH
2Hdmmod + Cu(NO3 )2 2KNO3 + H2 O
EtOH/H2 O
11.2 Metal Amides
+ Cu(dmmod)2 (42)
This class of compounds was, until recently, almost
The barium bis(dmmod) complex is readily prepared by completely unexplored for the group 2 elements. Lapperts
a redox reaction combining elemental barium with Hdmmod treatise on metal amides gives brief mention to the existence
(equation 43). Purified by distillation of the excess Hdmmod, of such species.84 Although the compounds have not yet been
Ba(dmmod)2 was identified to be authentic by elemental proven as precursors for metal oxides, several examples of
analysis, and found to be monomeric in benzene solution. compounds employing the bis[bis(trimethylsilyl)] ligand were
Examination of the literature reports currently available discussed above in the section on compounds formed between
indicates that this represents the first observation of an group 2 elements and group 15 elements. Perhaps there will
ambient condition liquid barium compound that is based on be some additional work here, which is directed towards SMO
-diketonate ligands.81 Utilizing the data, it would appear that CVD, that will eventually come out from this same approach.
the metal center is six coordinate. Examination of space-filling
molecular models lends some credence to this suggestion.
11.3 Metal Carboxylates
Ba + xs Hdmmod Ba(dmmod)2 + H2 (43)
Apblett and Gueorguieva85 have investigated the synthesis
of novel low-temperature metal organic deposition precur-
Although not reported as anhydrous compounds,
sors for BaO, Y2 O3 , and CuO. Substantial improvement in the
Ba(L)2 (H2 O)n have been prepared for HL = Htmmhd (10)
pyrolysis process over simple carboxylates has been realized
and Hdmmhd (11).
via the rational design of the molecular precursors so that
the ligands decompose readily into small, volatile fragments.
One promising ligand is Hhipa (12), the metal complexes of
O O O O which are readily prepared by reaction of the metal chlorides
MeO MeO with the sodium salt of the carboxylate (equation 44). The cal-
t-Bu i-Pr cium compound [Ca(hipa)2 (H2 O)] has been characterized
(10) (11)
O(7)
11 ADDITIONAL GROUP 2 ELEMENT
COMPOUNDS
Ca
While research into SMO film growth has been conducted O(5)
almost exclusively with the above-described bis(-diketonate) O(6)
complexes, an emerging emphasis is being placed on the O(1)
development of alternative classes of group 2 compounds;
N(2)
some of these new efforts are discussed here. O(2)
O(6)
N(1)
11.1 Metal Halides
by X-ray crystallography (Figure 13). components demands the presence of a viable processing route
to electronically pure material. Traditional ceramic methods
MClx + xNa(hipa) M(hipa)x + x NaCl (44) (see Ceramics) for powder compaction, followed by organic
binder burnout, serve unsatisfactorily in this capacity.89
Bulk single-crystal growth for all necessary compositions
OH OH is not yet mature enough to provide the quantities of high
N N
quality material demanded for evaluation purposes. Thus,
HO investigators have been forced to examine alternate synthetic
CO2H Ph
schemes. Closed space vapor transport is, in general, not well
Ph
suited to metal oxide growth. It does not appear that any work
(12) (13) has been reported in the area of liquid phase epitaxy of these
systems. Certainly, this would be a worthy pursuit and should
All of these complexes decompose cleanly at low temper- be explored for its potential.
ature to produce acetonitrile, carbon dioxide, and initially, the
metal hydroxide (equation 45). The decomposition tempera-
tures are 144, 176, and 198 C for Ba, Cu, and Y, respectively.
In the case of copper and yttrium, the final product is the metal 13 GROUP 2 ELEMENT ALKOXIDES
oxide produced by the dehydration of the hydroxide, while
barium hydroxide recombines with carbon dioxide to yield While the earliest work in this area was from
the carbonate. Barium carbonate formation can be avoided, Bradley,90 Chisholm and Caulton, and their group,
however, by use of a different ligand that avoids carbon diox- have recently prepared both cluster alkoxides and
ide formation. Benzoin -oxime (Hbo) (13) has been found siloxides that have some increased solubility proper-
to be a quite suitable diprotic ligand for this purpose. The ties, for example, HBa5 (O)(OPh)9 (THF)8 , H3 Ba6 (O)(O-t-
barium salt is easily prepared by reaction of the oxime with Bu)(OCEt2 CH2 O)(THF)3 ,91 H4 Ba6 (6 -O)(OCH2 CH2 O
the metal dihydride (equation 46), and it decomposes cleanly Me)14 ,92 Ba3 (OSiPh3 )6 (THF),93 and Ba(Hdbp)2 (OCH2 CH2
to barium oxide by loss of benzaldehyde and benzonitrile at NMe2 )2 (HOCH2 CH2 NMe2 )2 .94 However, as cluster aggre-
250 C (equation 47). gates, they both are coordinatively unsaturated and involatile.
The former is addressed by parasitic addition of reaction
R medium, whereas the latter is an intrinsic property and there-
N fore chemically unaddressable (see SolGel Synthesis of
(45)
HO O MOH + RCN + CO2 Solids). Oligomeric species have been prepared by Hubert-
M O Pfalzgraf 95 based on triethanolamine. Buhro96 has isolated
BaH2 + Hbo Ba(bo) + 2H2 (g) (46) a mega-cluster, Ca9 (OCH2 CH2 OMe)18 (HOCH2 CH2 OMe)2 ,
Ph
from short-tail base-stabilized alkoxides. This work has
N O recently been extended by Page to include mixtures of Ba, Y,
O Ph BaO + PhCN +
(47) and Cu for sol gel processing.97
Ph H The formation of the first monomeric heavy group 2
M O
element alkoxides has been postulated based on oligoether
ligands (14), the molecularity of which is supported by
The crown ether complexes (see Crown Ethers) of barium
cryoscopic molecular weight data.80 This contrasts with
carboxylates, Ba(O2 CR)2 (18-crown-6), have been isolated;86
the initial publications of Ba(OR)2 preparations.90 When a
however, no studies have been reported of their suitability as
saturated hydrocarbon is the parent alcohol, apparently only
BaO precursors.
involatile and insoluble alkoxides are formed. Quite recently,
a benzene soluble bis(aryloxide), Ba(bht)2 (THF)2 , has been
prepared; however, no volatility was reported.98
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Acad. Sci., Paris, 1991, 312 II, 983. Angew. Chem., Int. Ed. Engl., 1990, 29, 1483.
76. L. G. Hubert-Pfalzgraf, personal communication. 94. K. G. Caulton, M. H. Chisholm, S. R. Drake, and K. Folting,
77. A. Gleizes, D. Medus, and S. Sans-Lenain, Materials Research Inorg. Chem., 1991, 30, 1500.
Society, Spring Meeting, San Francisco, CA, 1992, Abstract 95. L. G. Hubert-Pfalzgraf, O. Poncelet, C. Sirio, and J. C. Daran,
N4.7/P3.7. in Chemical Processing of Advanced Materials, eds.
78. W. S. Rees Jr, C. R. Caballero, and W. Hesse, Angew. Chem., L. L. Hench and J. K. West, Wiley, New York, 1992, p. 277.
Int. Ed. Engl., 1992, 31, 735. 96. S. C. Goel, M. A. Matchett, M. Y. Chiang, and W. E. Buhro,
79. W. S. Rees Jr and D. A. Moreno, J. Chem. Soc., Chem. J. Am. Chem. Soc., 1991, 113, 1844.
Commun., 1991, 1759. 97. C. J. Page, C. S. Houk, and G. A. Burgoine, Materials
80. W. S. Rees Jr and D. A. Moreno, in Spectroscopy and Research Society Spring Meeting, San Francisco, CA, 1992,
Structure of Molecules and Nuclei, eds. N. R. Johnson, Abstract N1.4.
W. N. Shelton, and M. A. El-Sayed, World Scientific, London, 98. P. B. Hitchcock, M. F. Lappert, G. A. Lawless, and B. Royo,
1992, p. 367. J. Chem. Soc., Chem. Commun., 1990, 1141.
81. L. M. Tonge, D. S. Richeson, T. J. Marks, J. Zhao, B. W. 99. S. R. Drake, W. E. Streib, M. H. Chisholm, and K. G. Caul-
Wessels, H. O. Marcy, and C. R. Kannewurf, Adv. Chem. Ser., ton, Inorg. Chem., 1990, 29, 2707.
1990, 226, 351. 100. K. F. Tesh and T. P. Hanusa, J. Chem. Soc., Chem. Commun.,
82. T. Kimura, M. Ihara, H. Yamawaki, K. Ikeda, and M. Ozeki, 1991, 879.
Materials Research Society Fall Meeting, 1988, Boston, MA, 101. P. B. Hitchcock, M. F. Lappert, G. A. Lawless, and B. Royo,
Abstract F9.7. J. Chem. Soc., Chem. Commun., 1990, 1141.
83. K. Timmer and H. A. Meinema, Inorg. Chim. Acta, 1991, 187, 102. K. F. Tesh, T. P. Hanusa, J. C. Huffman, and C. Y. Huffman,
99. Inorg. Chem., 1992, 31, 5572.
84. M. F. Lappert, P. P. Power, A. R. Sanger, and R. C. Sri- 103. S. R. Drake, D. J. Otway, M. B. Hursthouse, and K. M. Abdul-
vastava, Metal and Metalloid Amides: Syntheses, Structures, Malik, Polyhedron, 1992, 11, 1995.
and Physical and Chemical Properties, Ellis Horwood,
104. L. B. Cole and E. M. Holt, J. Chem. Soc., Perkin Trans. 2,
Chichester, 1980.
1986, 1997.
85. A. W. Apblett, personal communication.
105. D. L. Huges and J. N. Wingfield, J. Chem. Soc., Chem.
86. J. M. Boncella, C. J. Coston, and J. K. Cammack, Polyhedron, Commun., 1977, 804.
1991, 10, 769.
106. K. G. Caulton, M. H. Chisholm, S. R. Drake, and K. Folting,
87. S. S. Flacher, J. Am. Chem. Soc., 1955, 77, 6194. Inorg. Chem., 1991, 30, 1500.
88. A. R. West, Solid State Chemistry and its Applications, 107. O. Poncelet, L. G. Hubert-Pfalzgraf, L. Toupet, and
Wiley, New York, 1984, p. 540. J. C. Daran, Polyhedron, 1991, 10, 2045.
89. W. D. Kingery, H. K. Bowen, and D. R. Uhlmann, Introduc- 108. S. R. Drake, W. E. Streib, K. Folting, M. H. Chisholm, and
tion to Ceramics, 2nd edn., Wiley, New York, 1976, p. 1032. K. G. Caulton, Inorg. Chem., 1992, 31, 3205.
90. D. C. Bradley, R. C. Mehrotra, and D. P. Gaur, Metal 109. A. P. Purdy, C. F. George, and J. H. Callahan, Inorg. Chem.,
Alkoxides, Academic Press, New York, 1978, p. 411. 1991, 30, 2812.
91. K. G. Caulton, M. H. Chisholm, S. R. Drake, and K. Folting, 110. A. P. Purdy, A. D. Berry, R. T. Holm, R. T. Fatermi, and
J. Chem. Soc., Chem. Commun., 1990, 1349. D. K. Gaskill, Inorg. Chem., 1989, 28, 2799.
92. K. G. Caulton, M. H. Chisholm, S. R. Drake, and J. C.
Huffman, J. Chem. Soc., Chem. Commun., 1990, 1498.
Alloys density functional (LDF) Schrodinger equations; metallurgists
regard atoms as fuzzy balls interacting via pair potentials.
These three approaches, the number of atoms that can be
Bill C. Giessen1 & Rafael Hidalgo2 treated by each of them, and the accuracy of the results
1
Northeastern University, Boston, MA, USA obtained are shown in Figure 1.4
2
Springfield Technical Community College, Springfield, MA, USA The second and perhaps most important reason is that the
central concept of alloy work, namely, the microstructure
and its modification by alloying and treatment, is not
a chemical concept; there is no equivalent for it in
1 Introduction 1 chemistry. Only recently, with the rising interest in solid-
2 Alloy Phases and Phase Diagrams 2 state chemistry, has this begun to change; chemists adopt the
3 Technical Alloys and Their Applications 4 band language,5 and, largely through the use of inorganic
4 Structural Intermetallics 6 compounds as precursors for microelectronic materials6
5 Selected Application: Specific Alloys 7 and the increasing involvement of chemists in ceramics
6 Preparation and Characterization 12 science,7 materials chemistry8 has become a branch of
7 Related Articles 12 inorganic chemistry. One may now anticipate an increasing
8 References 12 interest of chemists in the synthesis and properties of
metallic alloys, motivating the comprehensive treatment
presented here.
Tight
metals and alloys with respect to their crystal structures, binding
constitution, microstructure, and properties (especially, Hckel
mechanical) is the subject of physical metallurgy.2,3
Although physical metallurgy had one of its roots in the
theory of phase equilibria, which is a part of physical chemistry
(the other root of physical metallurgy was metallurgical Many-
body
practice), it is a fact that, until recently, alloy chemistry and potentials
the science of alloys have not been major research subjects of
inorganic chemists. This has at least two major reasons. First,
the languages of bond formation are different for chemists, 50 500 50 000
physicists, and metallurgists:4 chemists tend to think in terms Number of non-equivalent atomic sites
of Huckel theory based on the overlap of angularly dependent
valence orbitals represented in real space and are not very
Figure 1 Schematic representation of the decrease in accuracy
familiar with the physicists band structure language expressed with increasing number of nonequivalent atomic sites that can be
in reciprocal space; alloy theorists come from physics and treated computationally by different levels of approximation. (Ref. 4.
calculate cohesive and structural properties by solving local Reproduced by courtesy of D. Pettifor)
2 ALLOYS
Intermetallics are stoichiometric or nonstoichiometric or alloys, which is seen when the crystallite grain size
phases composed of two or more metallic components9 decreases into the nm range, forming nanometer scale or,
(with possible admixtures of nonmetals as stabilizers) that in short, nanocrystalline alloys with large proportions of
crystallize with structures other than those of their metallic noncrystalline material on the grain boundaries (Figure 2) and
components. In the following, reference is often made to new properties. Thus, nanocrystalline materials may exhibit
intermetallics, but in this article they will not be treated superplasticity,13 novel electronic properties,14 or enhanced
structurally further. hydrogen storage capabilities (see the following text).
The extent and type of solid solution formation depends The properties of an alloy are primarily determined by
on several parameters.2 If both component elements are those of its constituent alloy phases; however, as stated, the
isostructural and, in addition, similar in size, valence microstructure, that is, the phases grain size, perfection,
electron concentration, and electronegativity, a series of distribution, and so on, which is due to the thermal and
complete substitutional solid solutions may form across mechanical history of the alloy, plays a major, modifying role.
the diagram, as for VCr, NiCu, CuAu, and SbBi; It is in this area that modern methods of alloy processing have
otherwise, limited terminal solid solutions form which had their most visible results, as will be seen from the review
are substitutional for elements with a solute solvent size of specific types of alloys in Sections 3 5.
difference less than 15%, but may be interstitial for
element pairs with size ratios of more than 20%, for
example, for Fe(C) or Pb(Au) (here, the bracketed element
is the solute). 2 ALLOY PHASES AND PHASE DIAGRAMS
We also list three other alloy phase types of current
interest that are not treated here in detail. Quasicrystals
are alloy phases partially or completely lacking translational 2.1 Alloy Phases
symmetry (see Quasicrystals); they form both equilibrium
Alloy phases will be described structurally using the fol-
and nonequilibrium alloy phases. Metallic glasses10 lack
lowing multiple (and somewhat redundant) nomenclature:
crystalline symmetry entirely; they are always metastable and
Name(s); Prototype (Pearson Symbol, Structure Report Sym-
generally require gas-phase deposition or rapid solidification11
bol). As an example: CuZn (-CuZn, -brass); CsCl (cP2,
to be retained, although in some cases their equilibration
B2) type. (Note: The Pearson symbol already contains the
kinetics are so slow that they can be prepared in bulk from the
crystal system and Bravais lattice). Alloy phase compilations
melt (bulk metallic glasses).12
with structural data are available.15
A third alloy state of great current interest is the mixed
With reference to the classification of alloy phases given
state containing both crystalline and amorphous metals
above, only a small amount of structural information on
alloy phases is required for the alloys treated in this article.
Disordered solid solutions are based on the terminal elements
and therefore mostly belong to the three most common
elemental structure types: Cu (cF4, A1) type, Mg (hP2, A3)
type, and W (cI2, A2) type. Following very common usage,
these three types are also occasionally referred to in the text as
fcc (=face-centered cubic), hcp (=hexagonal close packed),
and bcc (=body-centered cubic), respectively, although the
rigour of these designations leaves something to be desired.
The alloy phases of interest in the following sections on
commercial and developmental alloys will be introduced as
they are treated.
Next, the current status of the theoretical understanding of
alloy phases is reviewed. The techniques available for first-
principles calculations for alloys (and alloy phase equilibria)
up to the 1990s are listed and reviewed by de Fontaine.16
Current thinking is reviewed by Pettifor17 who is also a
major contributor to the understanding of alloy properties by
fundamental computations.
For perfectly ordered crystals at absolute zero, solutions to
Figure 2 Atomic structure of a two-dimensional nanocrystalline the Schrodinger equation can be calculated on fast computers
material computed using pair interaction potentials. The atoms in
the central portions of the nanocrystals are indicated in black; atoms using density functional theory (DFT) based on the self-
in the nanograin boundary regions are represented by open circles. consistent local density approximation (LDA);17 simplifying
(Ref. 13. Reproduced by permission of Springer) procedures using different basis functions include augmented
ALLOYS 3
plane wave (APW), augmented spherical waves (ASW), the impulse came with the start of systematic crystal-structure
Korringa Kohn Rostoker (KKR), and the linear muffin-tin studies following the introduction of X-ray crystallography,
orbital (LMTO) methods, as well as further developments beginning in the 1920s.9 Since then, vast efforts have been
originating from these designed to include variable axial spent on the experimental determination of phase diagrams.
ratios. Transition metals can be handled by modern versions As a result, for common elements such as Fe, Cu, C, and so on,
of the tight binding (TB) approximation, which is derived almost every binary T x phase diagram is known; in the case
from the linear combination of atomic orbital (LCAO) method of many other elements, constitution diagrams are known at
well familiar to chemists (see LCAO Approximation), with least for their binary systems with some elements representing
semiempirical matrix elements derived from the LMTO every group of crystal chemically similar elements, such as
method and treated self-consistently. the early long period transition metals, noble (platinum group)
For disordered systems, the task is harder because metals, or the rare earth metals. Work on ternaries has also
translational symmetry is lost. The direct configurational proceeded well. Binary alloy constitution diagrams have been
averaging (DCA) method takes all possible local cluster compiled.21,22
configurations of given stoichiometry into account and From an economic viewpoint, the classical determination
averages them; to obtain manageable computation times, of alloy phase diagrams is a laborious process, involving alloy
this method is used in connection with the relatively preparation and heat treatment, compositional, structural, and
simple TB method and hence applies best to transition microstructural analysis (and, even then, not yielding reliable
metals. Alternatively, average atoms are created to restore phase boundary information at low temperatures due to kinetic
translational symmetry, leading to the coherent potential limitations). While this investment is justified for alloys of
approximation (CPA), a mean-field technique that is used in major technical importance, the need for better economics has
connection with TB, KKR, or LMTO ASA (ASA = atomic driven an effort to use alternative methods of phase discovery
sphere approximation).16 such as multiple source, gradient vapor deposition or sputter
Introduction of partial order at finite temperatures adds deposition followed by automated analysis; alternatively,
another level of complexity and difficulty. This situation is multicomponent diffusion couples are used to map binary
handled by the cluster variation method (CVM) free energy or ternary alloy systems structurally and by properties (see
functional, which is expressed as a function of multisite Section 6). These techniques have been known for decades,
correlation functions, whose coefficients are obtained by the but they have been reintroduced more recently as high-
generalized perturbation method (GPM) or the embedded efficiency methodologies to create compositional libraries
cluster method (ECM). All of these methods are highly by a combinatorial approach,23 inspired perhaps by the recent,
computationally intensive; at present, this area is probably general introduction of combinatorial methods in chemistry.
the principal frontier of alloy phase theory. Until recently, one might have considered this immense
To work around the complexities of these calculations collection of experimental information as one of the major
(which greatly multiply when multicomponent systems are experimentally gathered, but theoretically unexplained, bodies
involved as is the case in superalloys, see Section 3.3) of data in all of the chemical sciences. As shown above,
an empirically useful method of alloy phase prediction, however, in recent years major progress has been made
PHACOMP, has been developed;18 its predictions are based on the theory of alloys and in establishing empirical or
on electron concentration rules, especially d-electron shell semiempirical correlations for alloy phase formation; this, in
hole concentrations (see Section 3.3). turn, has benefited phase diagram prediction, which remains an
An attractive, semiempirical application of physical insight important goal of computational alloy theory. Two principal
into alloy formation is found in classifications of alloy phase approaches exist, which are presently in the process of slow
data into structure maps, quantum diagrams, and so on (see convergence.
Structure & Property Maps for Inorganic Solids) where a In the ideal case, one would have ab initio calculations
necessarily limited number of coordinates (one to three) must (such as those described above) for all competing crystalline
reflect the physical parameters determining the property of phases and the liquid (or liquids) involved, yielding their free
interest. An example is given below in the Pettifor map for energies as functions of composition and temperature and
TiAl intermetallics.4,19 Further developments in the mapping enabling standard common-tangent constructions to be made.
of intermetallics are due to Ceder.20 However, since up to now first-principles calculations having
the accuracy required to differentiate between competing
2.2 Phase Diagrams, Determination, and Computation phases are only possible for crystalline phases, complete
phase diagrams (which must include the liquid) cannot yet
Phase diagrams provide the thermodynamic foundation for be handled in this way.4,16 Nonetheless, it is very valuable
all alloy work by presenting the equilibrium constitution of to be able at least to calculate the solid-state portion of
alloys. Systematic phase diagram studies were first initiated relevant phase diagrams, thereby obtaining information about
about 100 years ago, when the thermodynamic foundations metastable phases, phase boundaries, phase decompositions,
of phase diagrams were being established; an additional and ordered phases (superstructures) that are not measurable
4 ALLOYS
experimentally because of slow kinetics at low temperatures. observed and calculated CoV phase diagrams is shown in
While this field of work is just opening up, it can be expected Figure 3.25 To construct this diagram, the existence and struc-
to produce important results. tures of the intermediate phases Co3 V, , and CoV3 were
At present, inclusion of the liquid into such calculations considered as given; the pair potential (PP) approach men-
requires use of fitted free energy curves, such as those used tioned in Section 1.1 as preferred by metallurgists has been
in the more empirical approach described below, but as liquid used in the energy computation.
alloy theory advances, this situation will improve. Thus, Pettifor17 showed how density functional theory (DFT,
complete phase diagram calculations based on pseudopotential see above) may strengthen the CALPHAD conclusions
calculations have been presented by Hafner.24 for complex alloy systems by providing information on
The other approach, which so far has had the greater compositionally nearby metastable alloy phases that may
practical impact, is primarily empirical. The CALPHAD (from affect alloy properties.
CALculated PHAse Diagrams) approach was pioneered by
L. Kaufman,25 a more recent presentation is by Saunders
and Miodownik26 The work of the CALPHAD group
focuses on calculations based on thermochemical data such 3 TECHNICAL ALLOYS AND THEIR
as those compiled by the Scientific Group Thermodata APPLICATIONS
Europe (SGTE),27 the ASM NBS Alloy Phase Data Activity,
PHACOMP (see above), and CALPHAD itself, but also In the following, a survey of the principal types of alloys
uses the results of ab initio structural energy calculations in current use is provided, with emphasis on those alloys
for elements and compounds as these become available. designed for advanced metals technology, as well as the
Phase diagrams are calculated from these data using reg- directions of current development. An excellent introductory
ular solution or other appropriate solution models. Some of source on these alloys and on further developments in this
the great strengths of the CALPHAD approach are that it area is Smith,28 from whom much in this section is drawn.
provides immediate, approximate diagrams for new systems
of interest and that it can be readily extended to ternary and
higher order systems that would be prohibitively complex 3.1 Steels
and expensive to study experimentally. A comparison of the
Steels of many types constitute 90% of the worlds use of
metals. Carbon steels are the backbone of the steel industry;
T (K)
Liquid (L) 1600
1800 L+d
d
S+A S+B 1400 L + Fe3C
1200 fcc (A) bcc g +d Liquid
Sigma (S) (B)
1200 L+g 1148 C
600 hcp S + Co3V g Austenite
(E) 1000 2.0 4.3
Temperature (C)
1200 Fe3C
S B 200
+ S +
600 Co3V V3Co
E
0% C 1 2 3 4 5 6 6.67
100%Fe Fe3C
(b) Co V Weight % carbon
Figure 3 CoV phase diagram: (a) calculated by CALPHAD Figure 4 The FeFe3 C metastable system underlying the carbon
methodology, (b) observed. (Ref. 25. Reproduced by kind permission steel making technology. (Ref. 28. Reproduced by permission of
of Springer Science & Business Media) McGraw-Hill)
ALLOYS 5
the underlying FeC phase diagram (Figure 4) is therefore first observed in 1906 in binary AlCu alloys. An alloy
without doubt the most important alloy constitution diagram. constitutional requirement for age hardening is a terminal
Its features include the wide phase field of fcc Cu (cF4, solid solubility (e.g. of Cu in Al) that sharply decreases with
A1) type -Fe (austenite), which terminates in a eutectoid decreasing temperature, allowing nonequilibrium precipitates
decomposition of austenite into bcc W (cI2, A2) type -Fe (GP zones) to form from a supersaturated Al-base solid
(ferrite) and the (metastable) compound Fe3 C (oP16, DO11 ) solution (age hardening). Thus, the solubility of Cu in Al
type (cementite). Much of the art of steelmaking consists of decreases from 5.65% at 548 C to <0.2% at 20 C.
controlling and modifying the formation of this eutectoid, or The complex Al alloys mentioned above are the mainstay
preventing it altogether by formation of the hard and brittle of the airframe industry; however, the search for ever lighter
tetragonal martensite phase (see also Hornbogen29 ). and stronger Al alloys has recently led to the development
Alloy steels form the next category; they contain small of aluminum lithium alloys (with 2% Li), which have a
levels (up to about 3%) of transition metal additives such as 10% higher elastic modulus and an 8% lower density than the
Ni, Cr, Mo, Mn, or Si in addition to C; the principal effect of current major high-strength aircraft alloy. Although elemental
these elements is to increase hardenability and toughness, for Li has a low density of 0.5 g cm3 and is a soft, low-melting
example, by influencing martensite formation. Even higher metal, upon introduction into an AlCuMg alloy it is quite
alloying contents, especially of Cr (up to 25%) and Ni (up beneficial to the strength-to-weight ratio. Unfortunately, this
to 20%) are used to obtain ferritic, martensitic, or austenitic improvement is also expensive: due to the difficulties of
stainless steels (with Cr favoring ferrite and Ni promoting manufacture and the cost of Li, AlLi alloys have a price
austenite formation); the principal wrought austenitic stainless several times that of the alloys they replace.30
steel (AISI-304) contains 19% Cr, 9% Ni, and <0.08% C. Amorphous Al alloys have been prepared by rapid
Despite the maturity of the steelmaking field, process- solidification processing (RSP, see 6.); nanostructural alloys
ing advances continue to be made. Thus, intricate thermal prepared from these glasses10 have potential applications as
processing paths designated by self-explanatory terms such as high-strength, low-density alloys.31
austempering and marquenching have improved the impact
resistance of plain-carbon steels. Further, two classes of high-
strength, low-alloy (HSLA) steels have been developed in 3.3 Superalloys
recent years, and such steels now play important technolog-
This is the generic name for a class of Ni-, Co-, or NiFe-
ical roles. In one case, microalloying (of plain-carbon steels)
based, heat-resistant alloys with high strength at high tem-
with very small amounts of strong carbide formers such as Nb,
peratures (up to 1100 C). We focus here on Ni-based super-
Ti, and V has given these steels a finer grain structure associ-
alloys. They typically contain 15 20% Cr, 15% 20% Co,
ated with much greater strength (making use of a general linear
4 10% Mo, 1 5% Al, 2 4% Ti and 0.05 0.20% C, and they
correlation between yield strength and the reciprocal square
derive their strength from the presence of a fine dispersion
root of the grain size; this is the Hall Petch relationship).3
of refractory metal or Cr carbides of compositions M6 C,
Another new class consists of dual-phase steels containing
M23 C6 , and MC, an oriented precipitate such as Ni3 (Al,
hard martensite in a soft ferrite matrix, producing high val-
Ti) that is coherent with the Ni solid solution matrix, and the
ues of tensile strength and total elongation. Maraging (from
absence of deleterious phases such as cellular carbides and
martensite and age hardening) produces ultra-high strength,
embrittling phases. The latter is a complex, tetrahedrally
structural low-C steel with 18% Ni, 10% Co, 4% Mo, and
close-packed (or Frank Kasper) phase.32 The elimination of
1% Ti by aging a highly martensitic steel at 500 C for several
the phase in modern superalloys was an early example
hours, thereby forming ultrafine strengthening zones of Ni3 Mo
of the use of an electron theoretical (and, with hindsight,
and Ni3 Ti lying along dislocations and martensite lath bound-
somewhat oversimplifying) concept in alloy design: it had
aries. Finally, in the area of stainless steels, ferritic austenitic
been noted that the phase occurred at a specific range
duplex structures have also produced an incremental property
of the average number of d-electron shell holes; subsequent
improvement in yield strength and corrosion resistance.
alloys were designed such as to avoid this hole concentration
Combinations of sophisticated alloying and thermal
range and thus to avoid phase formation. The PHACOMP
treatment thus continue to advance the science of mankinds
method18 mentioned above was specially designed for use
principal structural metal.
in such applications; semiempirical PHACOMP/CALPHAD
calculations have been used in gas turbine component alloy
3.2 Aluminum Alloys development work involving alloys with up to 9 functional
elemental components.33
Wrought heat-treatable Al alloys contain Mg, Zn, and Superalloys are continuously being developed further for
Cu on the level of several percent as precipitation and use at ever increasing temperatures (Figure 5) in response to
solid solution hardening ingredients. The precipitation process the need for running engines at higher temperatures to increase
forms nanometer size Guinier Preston (GP) zones that are fuel efficiency.34 Milestones in the advancement of superalloy
coherent with the matrix and produce the age-hardening effect technology were reached with the development of directional
6 ALLOYS
Directional
structures
and Al, Ti alloys have been developed for many uses in
g / g- d Eutectic
1100 aerospace and the chemical industry. The principal currently
used alloy is an Ti alloy with 6% Al and 4% V; the
Temperature (C)
DS
DS MAR-M200 + Hf
next most commonly manufactured form is commercially
1000 IN100 pure, unalloyed Ti, which is also used in surgical implants.
Vaccuum
RENE 80 CAST
melted
Recent developments include multicomponent alloys such as
UDIMET 700
900
the low-creep rate Ti-1100 alloy (with 6% Al, 2.75% Sn,
Wrought
WASPALOY
4.0% Zr, 0.40% Mo, and 0.45% Si) for jet engine compressors
and the age-hardened Beta-C alloy (3% Al, 8% V, 6% Cr,
NIMONIC alloy 80A Air melted
800 4% Mo, 4% Zr) with high corrosion resistance for high-
temperature chloride environments.35
1940 1950 1960 1970 1980 1990 2000
Year
3.5 Cemental Carbides
Figure 5 Progress in high-temperature engine component alloy These materials are extremely hard and wear resistant up to
development as a function of date, as measured by use temperature.
high temperatures (800 C) and are used as high-speed cutting
The figure represents the service temperature at which a rupture life
of 100 h would be obtained under a stress of 138 MPa. (Ref. 34. tools. They contain finely dispersed (1 3 m size) particles
Reproduced by kind permission of Springer Science & Business of W, Ti, or Ta carbides (primarily WC) in a cobalt binder
Media) matrix (70 97.5% carbide). The direction of further develop-
ment here is to produce and compound increasingly fine partic-
ulates, for example, by use of chemical precursor processes.36
4 STRUCTURAL INTERMETALLICS
A
Sc Y La Zr Hf Ti Ta Nb V W Mo
Si
Ge
Sn tP4 CuAu 12/12
Pb cP2 CsCl 14/14
Ga tP2 CuTi 14/14
B Al
oP8 FeB 17/9
In
Tl oC8 CrB 17/9
Zn cP8 FeSi 13/13
Cd
Hg
x = 0.5
Sc Y La Zr Hf Ti Ta Nb V W Mo Sc Y La Zr Hf Ti Ta Nb V W Mo
tI24 HfGa2 12/12
Si Si
Ge tI6 MoSi2 14/14 Ge
Sn hp, oF Cr,TiSi2 14/14 Sn
Pb cF, hP Laves 16/12 Pb
Ga tP30 Sigma 14/12 Ga
Al tI12 CuAl2 Al
15/10
In In
oF48 CuMg2 15/10
Tl Tl
hP3 AIB2 14/11
Zn hP6 Zn
Ni2ln 11/14
Cd Cd
Hg oCl2 ZrSi2 10/8,8 Hg
x = 0.33 x = 0.67
Si Si
Ge Ge
Sn cp4 Cu3Au 12/12 Sn
Pb 12/12 Pb
tI8 Al3Ti
Ga Ga
tI16 Al3Zr 12/12
Al Al
In hP8 Ni3Sn 12/12 In
Tl cP8 Cr3Si 12/14 Tl
Zn tP32 Ti3P 9/14 Zn
Cd Cd
Hg Hg
x = 0.25 x = 0.75
Si Si
Ge Ge
Sn Sn
cI2 W 14
Pb Pb
cF4 Cu 12
Ga tI2 In 12 Ga
Al hP2 Mg 12 Al
In hP4 aLa 12,12 In
Tl cF8 C 4 Tl
Zn Zn
Cd Cd
Hg Hg
A1x Bx
x =0 x =1
60
state of normal (nonsuperconducting) regions containing
the magnetic flux (flux lattice) and superconducting regions
50
carrying the supercurrent.
Currently used magnet coil alloys are of two kinds:
40
NbTi solid solutions with Tc < 9.5 K and Hc 10 T and
intermetallic compound superconductors with the Cr3 Si (cI8,
30
A15) type structure shown in Figure 10, such as Nb3 Sn
with Tc = 18.3 K and Hc 15 T; even larger Hc values
20
are possible. In NbTi the flux lattice is pinned by defects
10 introduced by a high degree of cold working that occurs in
the course of drawing the alloy rods clad in copper into a
0 complex, multistrand wire. For the brittle A15 type materials,
0.04 0.08 0.12 0.16 0.20 drawing in this way would introduce cracks; the compound
Boron concentration (wt %) is therefore formed in situ by a diffusion process combining
Nb cores and Sn supplied either by a pool of Sn or a CuSn
bronze matrix. An actual wire with a diameter of 1 2 mm
Figure 9 Enhancement of tensile elongation and change of fracture made by this process is composed of thousands of filaments
type of Ni3 Al (with 24 at. % Al) by small boron additions. (Ref. 43. formed into bundles.50
Reproduced by kind permission of Springer Science & Business
Media)
5.3 Shape Memory Alloys (SMAs) and Magnetostrictive
Alloys
Hard (permanent) magnet materials have advanced from
hardened steel via cast Alnico (iron aluminum nickel Certain intermetallics, among them stoichiometric NiTi
cobalt) magnets to modern AB5 and A2 B17 rare earth cobalt and some CuZn-based phases, transform from a high-
alloy magnets such as SmCo5 and Sm2 Co17 , which are symmetry elevated temperature phase (CsCl type for NiTi) to
made from powder particles compacted in a magnetic field
and subsequently sintered to fully bring out their magnetic
anisotropy. The SmCo5 magnetic compound has the hexagonal
CaCu5 structure discussed and shown for LaNi5 in the
section on hydrogen absorbing alloys, below. A further
advance in this area was the discovery and development47
of the compound Fe14 Nd2 B, which can be made by rapid
solidification processing, grinding the melt-quenched ribbons,
and hot pressing the powder to final shape. These high-energy-
product magnets are now widely available at low cost.
a lower-symmetry room-temperature form by a diffusionless that can sense their environment and adapt their properties
martensitic shear transformation.43,51,52 The TiNi alloy is to it. SMAs are industrially manufactured for applications as
especially prominent under the designation NITINOL.53 sensors, actuators in safety devices, spacecraft and automotive
These martensites have a large plastic deformability such parts, and medical devices such as vascular implants (stents),
that an SMA wire or sheet can be deformed into an arbitrary blood vessel screens and probes.54
shape at ambient temperatures, for example, made into a Magnetostrictive alloys form a subset of shape memory
loop. Upon heating and reversal to the cubic form, the alloys; they undergo reversible martensitic transformations
part regains its original shape. In some properly trained upon application and reversal of magnetic fields, resulting in
SMAs the reversible shape change occurs on cooling and large recoverable strains. Such alloys are useful as sensors and
subsequent reheating of the alloy. The martensites responsible activators; a typical, widely used magnetostrictive sensor alloy
for this remarkable effect form in lenticular shapes or laths is TERFENOL-D (Tb1x Dyx Fe2 ) for which the strain is about
as seen in Figure 11(a) for an FeNiAl SMA that exhibits a 0.2%; large values (up to 6% in some experimental alloys
fractal behavior of self-similar lenses on ever-smaller scales, such as Ni2 MnGa) are evidence of giant magnetostriction.55
as shown in Figure 11(b) together with a measurement of
the pertinent fractal dimension.43 SMAs with their complex
thermomechanical behavior are perhaps among the first alloy 5.4 Hydrogen Absorbing Alloys
representatives of intelligent materials or smart materials
A number of pure metals and alloys form hydrides with
densities of hydrogen atoms per unit volume exceeding that of
liquid hydrogen (Table 1),56 suggesting their use as hydrogen
10 m storage media for hydrogen-based energy applications such
as automotive systems.57 Further, the reversible uptake of
hydrogen can be used to form the anode (negative terminal)
in secondary (storage) batteries as a hydrogen charged (metal
hydride) electrode.
To be useful for storage, a candidate alloy should have
a room-temperature hydride dissociation pressure in the
range of 1 2 atm, with a pressure plateau ranging up to
a stoichiometric ratio of hydrogen:metal 1, with good
resistance to degradation of these properties on cycling
and with a reasonable materials cost. These conditions are
best met by intermetallics such as FeTi, NiTi, Mg2 Ni, and
LaNi5 , which combine an early group element having a
(a)
large negative enthalpy of hydride formation with a late
transition element having a small positive enthalpy, thus
reducing the compounds enthalpy of hydride formation into
the range appropriate for the desired dissociation pressure;
possibly, the Fe or Ni component also catalyzes the reaction.
2 3
(Enthalpy of formation is the dominant component-variable
n = 1/2 term in the Gibbs free energy of hydride formation, the
N=3 entropy of the process being uniformly large and negative.)
D = 1.58
Density Atoms of
(b) x=1 x=2 x=3 x=4
Medium (g cm3 ) Wt % of H H/cm3 (1022 )
H2 (liquid) 0.07 100 4.2
H2 (gas, 150 atm, 20 C) 0.012 100 0.38
Figure 11 (a) Fractally distributed martensite phase (dark) and NH3 (liquid) 0.6 17.7 6.5
residual, untransformed austenite phase (light) in an FeNiAl MgH2 1.4 7.6 6.7
shape memory alloy (SMA); (b) (top row) schematic representation TiH2 3.8 4.0 9.1
of the fractal fragmentation of austenite crystallite by martensite VH2 2.08 11.37
formation, resulting (top right) in the structure shown in (a); (bottom Mg2 NiH4 2.6 3.6 5.6
row) a fractal process of dimension D = 1.58 (Sierpinski triangle) FeTiH1.74 FeTiH0.14 1.52 5.5
shown for comparison. (Ref. 43. Reproduced by permission of LaNi5 H6 8.25 1.37 6.76
Springer)
ALLOYS 11
10 55C
to degradation and deactivation and is currently preferred for
40C secondary batteries. To lower the price of LaNi5 , La can be
30C
replaced by Mischmetal (M), a less expensive, commercial
mixture of unseparated rare earth metals with about 50% Ce,
30% La, and 15% Nd, the rest consisting of the other 10
stable rare earth metals. This replacement, however, raises
the plateau pressure and requires additional alloying with Ca
0C
(substituting for M) and elements chosen from the group
1 Fe, Co, Mn, Cu, or Al (substituting for Ni) to modify
the plateau pressure back to acceptable values.59 Practical
hydrogen absorbing alloy systems thus require complex alloy
chemistry. In advanced FeTi type bcc alloys such as Ti-V-Mn
and Ti-V-Cr, up to 2 H atoms per metal atom can be reversibly
absorbed.60
This field receives additional attention as the interest in a
hydrogen fuel economy increases; a recent review comparing
0.1 storage of H in alloys with that in other media is found in
0 0.2 0.4 0.6 0.8 1.0 1.2 Ref. 57.
Composition (H/M)
A representative isotherm plot is shown for FeTi in New technologies are advancing the age-old methods for
Figure 12.58 giving alloys high surface hardness for wear resistance and
FeTi and NiTi have the ordered CsCl (cP2, A2) type fatigue resistance, while retaining the toughness and strength
structure shown in a different context for AlNi in Figure 5. of the core.28 Traditional induction thermal methods have
LaNi5 has the hexagonal CaCu5 (hP6, D2d ) type structure now been joined by the capability for laser treatment; the high
12 ALLOYS
energy density of the laser beam and the self-quenching aspect (AEM). High-resolution transmission electron microscopy
of the process, where the workpiece itself acts as an efficient (HRTEM)73 and scanning transmission electron microscopy
cooling medium, have combined in research arrangements (STEM) permit resolution into the 0.1 and 0.2 nm range,
to produce local cooling rates as high as 108 C/s. If alloys respectively; corresponding micro-diffraction data for local
are surface-melted under these conditions, metastable phase structure analysis are obtained by convergent beam elec-
formation may result.63 tron diffraction (CBED). These structural methods are further
Glow discharge of plasmas as a means of producing supported by submicron volume chemical analysis, by elec-
reactive ions for enhanced surface reaction are exploited tron energy loss spectroscopy (EELS) and atom location
in the ion nitriding64,65 and ion carborizing66 processes. The by channeling-enhanced microanalysis (ALCHEMI),74 sup-
rather complex surface and near-surface gas-phase chemistry plementing the standard method of energy dispersive X-ray
may involve gas reactions with sputtered surface ions and emission spectroscopy (EDS).73 Three-dimensional atom dis-
redeposition of the product.66 Other coating technologies tribution probes (3DAPs), a further development of field ion
include ion implantation of Ti or N to improve fatigue microscopy (FIM), permits atomic-scale materials analysis.75
resistance in steels, physical vapor deposition (PVD) and An overview of methods for surface and interface analysis
plasma-assisted PVD to produce hard TiN coatings,28 and of metals and alloys is available.76 Important atomic-
boridation.67 scale surface structure information can be gathered by
Corrosion and corrosion protection of pure metals form a scanning tunneling microscopy (STM) or scanning atomic
vast field not covered here. For alloys, corrosion may involve force microscopy (SAFM), complementing scanning electron
de-alloying (preferential loss of one constituent) if they have microscopy (SEM), field ion microscopy (FIM), and small-
different electrochemical potentials;68 such processes have angle neutron scattering (SANS).69
been modeled on the atomic scale by Monte Carlo methods.69
More generally, with greater understanding of bulk
properties, interest in alloy surface processes and their
dynamics has risen.70
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Academic Publishers, Dordrecht, 1992, p. 37. 39. D. G. Pettifor, in Intermetallic Compounds, Structure and
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Aluminum: Inorganic aluminosilicates. Aluminum also occurs in numerous well-
known but rarer minerals such as spinel [MgAl2 O4 ], garnet
Chemistry [Ca3 Al2 (SiO4 )3 ], beryl [Be3 Al2 Si6 O18 ], cryolite [Na3 AlF6 ],
and turquoise [CuAl6 (PO4 )4 (OH)8 (H2 O)4 ]. Pure aluminum
oxide, Al2 O3 , is known as corundum while many impure forms
Allen W. Apblett of Al2 O3 occur naturally and find application as gemstones.
Oklahoma State University, Stillwater, OK, USA For example, sapphires and rubies are primarily composed
of aluminum oxide, but owe their distinctive colors to trace
impurities. In the case of rubies, chromium yields a red
color while titanium leads to the characteristic blue color of
1 Introduction 1 sapphires (the result of charge-transfer transitions involving
2 Preparation and Uses of Metallic Aluminum 2 the aluminum and titanium ions). Different concentrations
3 Aluminum Hydrides and Related Complexes 4 of various impurities produce a range of colors from quite
4 Aluminum Halides 5 pale, owing to low concentrations, to quite deep blue. Other
5 Aluminum Oxides and Hydroxides 7 colors include: purple and pink, yellow, orange, green, and so
6 Ternary and More Complex Oxide Phases 9 on. Chrysoberyl (BeAl2 O4 ) is both a useful gemstone and an
7 Aluminum Oxyacid Salts 11 important source for beryllium.
8 The Aqua Ions and Aqueous Chemistry 12 The high abundance of aluminum has resulted in a
9 Aluminosilicates 13 multitude of applications for the element and its compounds.
10 Aluminum Chalcogenides 13 Aluminum derives its name from alum, the double sulfate
11 Aluminum Pnictides 13 KAl(SO4 )2 12H2 O, which was used medicinally as an
12 Mixed Aluminum Chalcogenide Halides 14 astringent in ancient Greece and Rome. Today, aluminum
13 Aluminum Carbide and Borides 14 plays an important role as the pure metal and its alloys while
14 Alkoxides 14 its compounds have extensive applications as structural and
15 Aluminum Carboxylates 15 medical ceramics, electronic and optical materials, catalysts,
16 Related Articles 15 ionic conductors, coagulants for water purification, and
17 Further Reading 15 reagents for preparation of other chemicals.13
18 References 15 Chemically, aluminum exhibits typical metallic behavior
but it shows many similarities to boron. It combines with
almost all nonmetallic elements to form compounds with
aluminum in the +3 oxidation state. It also forms intermetallic
Glossary compounds with metallic elements from all groups of the
periodic table (see Alloys). Aluminum exhibits exceptional
Astringent: any substance or agent that causes tissues to affinity for oxygen and is often used as a reducing agent to
contract or that inhibits secretion of fluids such as mucus obtain Cr, Mn, V (see Thermite Reaction). Finely powdered
or blood aluminum metal explodes upon contact with liquid oxygen but
Friedel Crafts reaction: an alkylation or acylation of an ordinarily the metal is protected from reaction with oxygen,
aromatic using alkyl or acyl chlorides in the presence of a water or dilute acids by an adherent protective oxide film.
Lewis acid catalyst Complete reaction of aluminum may be accomplished by
Trityl: the Ph3 C+ cation amalgamation with mercury or contact with solutions of
salts of electropositive elements (e.g. HgCl2 ) that destroy the
oxide film. Aluminum dissolves readily in hot, concentrated
hydrochloric acid (equation 1) and in aqueous NaOH or KOH
1 INTRODUCTION at room temperature (equation 2).
Al(s) + 3HCl(aq) + 6H2 O [Al(H2 O)6 ]3+ (aq) + 3Cl (aq)
Aluminum, having an abundance of 8.3% by weight, is 3
+ H2 (g) (1)
the commonest metallic element in the Earths crust. It 2
occurs widely in igneous minerals such as feldspars and Al(s) + MOH(aq) + 3H2 O M+ (aq) + [Al(OH)4 ] (aq)
micas. Weathering of these has produced the clay minerals 3
such as vermiculite [Mg1.8 Fe2+ + H2 (g) (2)
0.9 Al4.3 SiO10 (OH)2 (H2 O)4 ], 2
montmorillonite [Na0.2 Ca0.1 Al2 Si4 O10 (OH)2 (H2 O)10 ], and
Al(OH)3 is amphoteric, behaving both as a Brnsted acid
kaolinite [Al2 (OH)4 Si2 O5 ]. The most commercially important
and base. Thus, freshly precipitated hydroxide is readily
mineral source of aluminum is bauxite [AlOx (OH)32x (0 <
soluble in both acid (equation 3) and alkali (equation 4).
x < 1)], which occurs in tropical and subtropical regions as a
result of exhaustive leaching of silica and other metals from Al(OH)3 (s) + 3H3 O+ (aq) [Al(H2 O)6 ]3+ (3)
2 ALUMINUM: INORGANIC CHEMISTRY
2[Al(H2 O)6 ]Cl3 Al2 O3 + 6HCl + 9H2 O (7) While aluminum occurs most commonly in aluminosilicate
minerals, its extraction from them is prohibitively difficult. It
Some physical and chemical properties of aluminum is therefore prepared from bauxite in a two-step procedure.
are presented in Table 1. As expected for the [Ne] 3s2 3p1 First, bauxite is purified by the Bayer process; this involves
configuration, the fourth ionization potential is prohibitively dissolution in aqueous NaOH, separation from insoluble
high. Therefore, the most common oxidation state of aluminum impurities (red mud containing Fe2 O3 ), and then precipitation
is three although compounds of aluminum(I) can be prepared. of Al(OH)3 by treatment of the solution with carbon dioxide.
However, the latter species quickly disproportionate to Calcining at 1200 C produces Al2 O3 , which is subsequently
elemental aluminum and aluminum(III) compounds. electrolyzed to produce aluminum metal. The electrolysis is
ALUMINUM: INORGANIC CHEMISTRY 3
the remaining two-thirds of the sodium atoms occupy the Mesitylene and xylenes interact more strongly, forming weak
12-coordinate A sites (see Oxides: Solid-state Chemistry). monomeric complexes, Br3 AlL. A typical strong complex
The sharing of two opposite vertices of AlF6 units, as in is formed by Me3 N, which forms both the tetrahedral 1:1
Tl2 AlF5 , leads to polymeric chains with AlF5 stoichiometry. complex (12) and the 1:2 trigonal bipyramidal complex (13).
In TlAlF4 and KAlF4 , AlF6 units share four equatorial vertices,
yielding layers with AlF4 stoichiometry. L L
More complex patterns of sharing vertices occur in Cl
compounds with intermediate stoichiometries. For example, Al Cl Al
Na5 Al3 F14 contains layers of Al3 F14 built up by one-third Cl Cl Cl
Cl L
of the AlF6 octahedra sharing four equatorial vertices and the
remainder sharing two opposite vertices. Na2 MgAlF7 contains (12) (13)
both AlF6 and MgF6 octahedra that are linked together by
sharing four vertices of the AlF6 units and all those of the Vibrational spectroscopy indicates that alkyl halides form
MgF6 units (see Fluorides: Solid-state Chemistry). weak RXAlX3 complexes. On the other hand, halides
As indicated earlier, Na3 AlF6 (cryolite) is the most that are readily ionized (e.g. trityl chloride) show a high
important aluminum fluoride since it serves as the solvent degree of charge separation and may be formulated as
for the electrolytic preparation of aluminum. R+ [AlCl4 ] . Acyl halides, RCOX, may coordinate through
Solid AlCl3 also contains six-coordinate aluminum. the halide atom, the carbonyl oxygen, or form ionic species,
The layered lattice exhibits a rapid increase in electrical RCO+ AlX4 . However, vibrational spectroscopy and X-
conductivity as the melting point (192.4 C) is approached, ray crystallography have not provided conclusive evidence
at which temperature it rapidly falls to zero. This coincides concerning the reactive species present in Friedel Crafts
with an 85% increase in volume, which results from a change alkylations in nonaqueous solvents.
in coordination of aluminum from six to four. The melt Aluminums tendency to form tetrahedral AlCl4 anions
consists of discrete Al2 Cl6 molecules (11). These molecules is exhibited in the formation of many interesting compounds.
predominate in the gas phase up to 400 C, beyond which they For example, the compound Cl3 AlClICl2 may be described
dissociate to trigonal planar AlCl3 monomers. as [ICl2 ]+ [AlCl4 ] . POCl3 reacts with AlCl3 to form three
types of compounds, the ordinary 1:1 and 2:1 complexes
X X X (where AlCl3 is O-bonded) and a third ionic species with
Al Al the unusual formulation[Al(OPCl3 )6 ]3+ [AlCl4 ]3 . Similarly,
X X
X AlCl3 reacts with THF to form [AlCl2 (THF)4 ]+ [AlCl4 ] while
(11) with acetonitrile, [(MeCN)5 AlCl]2+ [AlCl4 ]2 is obtained.
Crystalline salts of [AlCl4 ] may also be obtained by reaction
On the other hand, Al2 Br6 and Al2 I6 are both dimeric in the of alkali metal chlorides or [R4 N]Cl with AlCl3 in an organic
solid state as well as in the liquid and gaseous states. They also solvent. [AlBr4 ] and [AlI4 ] salts may be obtained in a
dissociate to monomers in the gas phase with Hdissoc = 59 similar manner.
and 50 kJ mol1 for the bromide and iodide, respectively. An oxonium salt may be readily prepared from the reaction
In all the dimeric Al2 X3 species, the terminal MX distance of AlCl3 with HCl in diethyl ether (equation 18). This is a
is 10 20 pm shorter than the bridging MX distance (Table 6). viscous oil similar to quaternary ammonium salt ionic liquids.
The external XMX angle is in the range 110 125 while Et2 O
the internal one is in the range 70 102 (see Hard & Soft AlCl3 + HCl [(EtO)n H]+ [AlCl4 ] (18)
Acids and Bases).9
Aluminum chloride/sodium chloride mixtures have been
The trihalides of aluminum are very strong Lewis acids,
much used as a molten salt medium (mp 173 C) for
and AlCl3 finds extensive use as a Friedel Crafts catalyst
electrolytic and other reactions.11 The principal equilibria
as a result of this. A wide variety of adducts are known
that occur in solution are given in Scheme 2.
and these exhibit an enormous range of stability, modes of
Conducting liquids are produced at room temperature by
bonding, structures, and properties.10 Aromatic hydrocarbons
the reaction of 1-methyl-3-ethylimidazolium chloride or N -
and alkenes only interact weakly but crystalline adducts may
butylpyridinium chloride with AlCl3 . These liquids are good
be isolated, for example, the clathrate complex Al2 Br6 C6 H6 .
1 A
X X X
X
+ 2
2 Al Al X Al X (19) B
X X 3
X X X
X
4 A
(14) (15)
(a) (b)
AlCl3 reacts with other metal chlorides such as CaCl2 ,
NbCl5 , NdCl3 , CrCl3 , or UCl5 to produce mixed halides with Al Vacant site Oxygen
halogen bridges, for example, Cl4 Nb(-Cl)2 AlCl2 (16). Many
of these complexes are very volatile; for example, the vapor
pressure of NdCl3 is increased by a factor of 1013 at 600 C. A Figure 2 Schematic representation of the structure of -Al2 O3 .
related reaction of AlCl3 with HgCl2 and mercury at 200 C (a) Pattern of occupancy by aluminum of the octahedral sites between
the hexagonal close-packed planes of oxide ions and (b) stacking
yields the molecular species Hg3 Cl2 2AlCl3 (17).
sequences of successive planes of aluminum atoms
Cl
Cl Cl Cl abrasives, refractories, and ceramics. Larger crystals when
Nb Al AlCl3 ClHgHgCl AlCl3 colored with metal ions are prized as gemstones, for example,
Cl Cl Cl
ruby (CrIII , red), sapphire (FeII/III , TiIV , blue), oriental emerald
Cl
(CrIII /VIII , green), oriental amethyst (CrIII , TiIV , violet), and
(16) (17)
oriental topaz (FeIII , yellow). Many aluminum-oxide based
gemstones are synthesized for use as laser materials. Indeed,
A wide range of aluminum compounds may be conve-
the first laser was created in 1961 by Theodore Maimanat
niently prepared from AlCl3 and alkali metal salts of various
using a rod of synthetic ruby as the lasing medium. Another
anions (equations 20 23).
example is alexandrite (chromium-doped chrysoberyl), which
LiY + AlCl3 AlCl2 Y + LiCl (20) is both a particularly attractive precious gem and a uniquely
2LiY + AlCl3 AlClY2 + 2LiCl (21) versatile solid-state laser material with the distinction of being
3LiY + AlCl3 AlY3 + 3LiCl (22) the first solid-state laser medium capable of tunable operation
at room temperature.
4LiY + AlCl3 LiAlY4 + 3LiCl (23)
Pure -Al2 O3 may be prepared by calcination of various
(Y = R, OR, NR2 , N=CR2 , H) Al salts, firing -Al2 O3 or any of the hydrous oxides above
Also, AlCl3 is a good transhalogenation reagent for 1200 C, and by the oxidation of aluminum metal. Often
the conversion of nonmetal fluorides to the corresponding single crystals of pure alumina that are prepared industrially
chloride; for example, BF3 to BCl3 (equation 24). are called sapphires. Large boules of synthetic sapphire
are grown by melting aluminum oxide above 2060 C and
BF3 + AlCl3 AlF3 + BCl3 (24)
then directionally cooling. The resulting synthetic sapphires
are anisotropic, monoaxial crystals that have a variety of
technological applications and are also gaining popularity
5 ALUMINUM OXIDES AND HYDROXIDES as gemstones known as white sapphires. Synthetic sapphire
is one of the hardest and strongest materials, and is rated
The oxides, hydroxides, and mixed oxyhydroxides of mechanically only second to diamond; It is one of the hardest
aluminum form an extended family of compounds that have materials available that when combined with a high modulus
immense technological importance.12 of elasticity and high tensile strength, makes it extremely
Al2 O3 occurs as the mineral corundum (-Al2 O3 ) and as wear, abrasion and impact resistant. For example, its abrasion
emery, a granular form of corundum that is contaminated stability is eight times higher than that of steel. It is colorless
with silica and iron oxide. In -Al2 O3 , the oxide ions form a with an optical transmission window that ranges from 190 nm
hexagonal close-packed array with aluminum ions regularly in the ultraviolet to 5 m in the infrared. It had good dielectric
distributed among the octahedral holes (Figure 2). It is a very qualities that make it a very good electrical insulator and it is
hard material (Moh 9) (see Mohs Hardness), has a high thermally very stable and does not lose any of its mechanical
melting point (2045 C), and is nonvolatile, inert, and a good and optical qualities from cryogenic temperatures to over
electrical insulator. As a result, it finds many applications in 2000 C. It has a thermal conductivity greater than most
8 ALUMINUM: INORGANIC CHEMISTRY
Bayerite, -Al(OH)3 , is not a naturally occurring mineral 6 TERNARY AND MORE COMPLEX OXIDE
but it can be made by precipitation from cold, alkaline solutions PHASES
(equation 25).
Numerous important mixed oxide phases are formed by the
2[Al(OH)4 ] (aq) + CO2 (g) 2Al(OH)3 (s)
combination of aluminum oxide and one or more other metal
+ CO3 2 (aq) + H2 O (25) oxides. The foremost of these from an industrial viewpoint are
spinels, -aluminas, and tricalcium aluminate, an important
Gibbsite, -Al(OH)3 , is a more stable form that is prepared constituent of Portland cement.
by slow precipitation from warm alkaline solutions or by
heating bayerite in aqueous sodium aluminate solution at
6.1 Spinels and Related Compounds
80 C. Both bayerite and gibbsite have layers of composition
Al(OH)3 formed by the sharing of Al(OH)6 octahedra in such Spinels are a large family of compounds that possess the
a way that a pair of close-packed OH layers are formed structure of the mineral spinel, MgAl2 O4 . The general formula
with aluminum atoms in two-thirds of the octahedral holes. is AB2 X4 and the unit cell contains eight of these formula
The two phases differ in the way the layers are stacked; units with the 32 oxygen atoms in a nearly perfect cubic close-
in -Al(OH)3 , it is approximately hexagonal close-packing packed array. In the normal spinel structure, eight A metal
but in the -form two out of three layers stack together atoms occupy tetrahedral sites while the 16 B atoms occupy
directly on top of each other (Figure 4). It should also be octahedral sites. Thus, the unit cell can be thought of as being
noted that a third form of Al(OH)3 , nordstrandite, has an composed of eight alternating cubic building blocks of ZnS
intermediate stacking arrangement between those of the - and NaCl type structures surrounded by an additional 14 A
and -forms. It is prepared by aging the gelatinous hydroxide atoms in a face-centered cubic array (Figure 5).
in the presence of a chelating agent such as ethylene glycol, Many spinel compounds adopt an alternative structure
ethylene diamine, or EDTA. As indicated earlier, gibbsite can where half the B cations occupy the tetrahedral sites while the
be dehydrated to boehmite at 100 C and to anhydrous -Al2 O3 remaining B cations and A cations occupy the octahedral sites.
at 150 C. It is also amphoteric, reacting both with bases and These are known as inverse spinels. The occupancy of the latter
acids (equations 26 28). Reaction with acids usually results sites may be random or ordered. The adoption of an inverse
in formation of the [Al(H2 O)6 ]3+ cation while those with spinel versus a spinel structure depends on a variety of factors;
base afford a variety of products such as [Al(OH)4 ] (18), the relative size of the A and B cations, the relative lattice
[Al2 (OH)10 ]4 (19), and [Al(OH)6 ]3 (20). energies, ligand-field stabilization, energies of octahedral
versus tetrahedral coordination, and polarization or covalency
Al(OH)3 (s) + 3H3 O+ (aq) [Al(H2 O)6 ]3+ (aq) (26)
effects. For example, in MgAl2 O4 one might expect the small
Al(OH)3 (s) + OH (aq) [Al(OH)4 ] (aq) (27)
4
HO H OH
OH
HO O OH
2 2OH Al Al
Al
HO OH HO O OH
HO HO OH
H
(18) (19)
O atoms
2OH (28) A atoms
B atoms
3
OH
HO OH
Al
HO OH
OH
(20)
Al3+ ion to occupy the tetrahedral site but this is outweighed by in nuclear reactors; BaAl2 O4 and CaAl2 O4 are also used as
the greater lattice energy associated with having the cation of supports for transition and lanthanide metal phosphors.
higher charge on the octahedral site, that is, (Mg)tet [Al2 ]oct O4 .
On the other hand, in NiAl2 O4 the crystal field stabilization 6.2 -Aluminas and Related Compounds
energy of NiII is greater in octahedral sites leading to a
disordered spinel; [Al0.75 Ni0.25 ]tet [Ni0.75 Al1.25 ]oct O4 . Sodium -alumina has achieved substantial importance as
Inverse and disordered spinels are called defect structures a solid-state electrolyte owing to its extremely high ionic
because all the identical crystallographic sites are not occupied conductivity (see Ionic Conductors).15,16 The compound has
by the same cation. A different defect structure is formed when the idealized formula of NaAl11 O17 (i.e. Na2 O11Al2 O3 ) and
spinels have disordered valencies. For example, the divalent only bears the name of -alumina because earlier studies either
cations in AB2 O4 may be replaced by equal numbers of MI and did not detect or ignored the presence of sodium. Indeed, it
MIII ions of appropriate size. As an illustration, the magnesium is the latter cations that stabilize the structure. This is closely
atoms of spinel may be replaced by lithium and aluminum related to spinel with no fewer than 50 of 58 atoms in the
atoms to give a spinel with formula LiAl5 O8 . This has a unit cell being arranged exactly as in spinel. The large sodium
defect structure in which two-fifths of the aluminum atoms atoms along with an equal number of oxygen atoms are
occupy all the tetrahedral sites: (Al2 )tet [LiAl3 ]oct O8 . Similarly, arranged in loosely packed planes between the spinel blocks.
disordering on the tetrahedral sites occurs in (MAl)tet [Al4 ]oct S8 There are several sites in the layer between the spinel blocks
where M = Ag+ or Cu+ . Valency disordering can also occur that the sodium ions can occupy, permitting rapid 2-D diffusion
when all the AII ions are replaced by MI , necessitating the of sodium in this plane and resulting in a low resistivity of
replacement of the BIII ions by MIV to achieve charge balance, 30 ohm cm. The structure can easily accommodate additional
for example, (Li)tet [AlTi]oct O4 . The possibilities of cation sodium ions and even single crystals often contain 20 30%
substitution are almost limitless, and cubic spinels such as more sodium than indicated by the idealized formula.
LiZn8 Al5 Ge9 O36 have been prepared.13,14 Sodium -alumina can be prepared by heating Na2 CO3 ,
As mentioned earlier, -Al2 O3 has a defect-spinel structure NaNO3 , or NaOH with any modification of alumina or its
in which not all the cation sites are occupied. This can hydrates to 1500 C in a sealed platinum vessel (to prevent
be thought of as being derived from spinel by replacing loss of Na2 O). The processing temperature may be dropped
magnesium by aluminum and maintaining charge balance by to 1000 C by addition of fluoride in the form of NaF or AlF3 .
leaving one site vacant for every three magnesium atoms The sodium is easily replaced by other metals (Li, K, Rb, CuI ,
replaced, that is, Al 64 [ ] 8 O32 . AgI , GaI , InI , or TiI ) by heating sodium -alumina with an
3 3 appropriate molten salt. The NO+ , NH4 + and H3 O+ salts have
The sensitive dependence of electrical and magnetic also been prepared.
properties of spinels on temperature, composition, and The -aluminas have been extensively used as permeable
detailed cation arrangement allows extensive tailoring of membranes in sodium sulfur batteries since they provide the
their properties for use in the solid-state electronics unique properties of allowing sodium transport but neither
industry. For example, CuAl2 O4 and CoAl2 O4 are used sulfur nor electron conduction and they are not attacked by
extensively in negative temperature coefficient resistors. molten sodium or sulfur.
Spinels are also employed in catalysis: NiAl2 O4 for Numerous other sodium aluminates are known including
methanation and dehydrogenation, FeAl2 O4 for oxidation a number of alkali-rich aluminates with quite different struc-
of chlorocarbons and ammonia production, CoAl2 O4 for tures from the -aluminas. Depending on stoichiometry, the
oxidation and desulfurization, and ZnAl2 O4 for oxidations solid-state reaction of -Al2 O3 with Na2 O at 700 C yields
of organics, aromatization, dehydrogenation, and cracking colorless crystals of Na5 AlO4 , Na7 Al3 O8 , and Na17 Al5 O16 .
and reforming of hydrocarbons (see Oxide Catalysts in Solid- Na5 AlO4 and the isoelectronic Li5 AlO4 contain discrete AlO4
state Chemistry). As well, ZnAl2 O4 and FeAl2 O4 are used in tetrahedra. Na7 Al3 O8 contains rings of six AlO4 tetrahedra
glass ceramics, Co2 AlO4 is used as a pigment in photography, that are linked together by four oxygen bridges to form an
Fe2 AlO4 as an absorbent for H2 S, and ZnAl2 O4 is used as infinite chain. Na7 Al15 O10 contains discrete chain anions,
an anticorrosion coating, an abrasive, a pigment, in moisture [O3 Al(OAlO2 )3 OAlO3 ]17 , formed by linking the corners of
sensors, and as a screen-printable dielectric compound for five AlO4 tetrahedra.17,18 Li5 AlO4 is an ionic conductor with
printed circuits. possible applications in batteries. It is also used as a blanket
When the divalent cation becomes too large for the spinel material in the nuclear power industry. MAlO2 (where M = Li,
structure to be adopted (e.g. Ca2+ , Ba2+ , and Pb2+ ), a tridymite Na, K) are prepared by reaction of Al2 O3 with the alkali metal
(SiO2 ) structure is obtained that has the divalent cation in carbonates at elevated temperatures. The latter two compounds
the interstices (see Silicon: Inorganic Chemistry). These have the NaFeO2 structure (see Iron: Inorganic & Coordina-
are synthesized by reaction of the oxides at temperatures tion Chemistry). NaAlO2 is used in water treatment, sizing of
over 800 C. The barium and calcium derivatives are used paper, and as a raw material for manufacture of zeolites, ceram-
in ceramics and refractories. In particular, BaAl2 O4 is used ics, and catalysts in the petroleum industry (see Zeolites).
ALUMINUM: INORGANIC CHEMISTRY 11
6.3 Calcium Aluminates has a very complex structure containing four, five, and six-
coordinate aluminum.
The calcium aluminates are an extensive family of
compounds that amply demonstrate the diverse structural
chemistry of aluminum. They are easily prepared by reaction
of CaO and Al2 O3 in appropriate ratios. 7 ALUMINUM OXYACID SALTS
Tricalcium aluminate is one of the components of
Portland cement (a mixture of 26% Ca2 SiO4 , 51% Ca3 SiO5 ,
11% Ca3 Al2 O6 , and 1% Ca4 Al2 FeO10 ). The structure of The propensity of aluminum salts to form the hexaaqua
Ca3 Al2 O6 contains a 12-membered ring composed of six-fused ion, [Al(H2 O)6 ]3+ , upon exposure to water requires that most
AlO4 tetrahedra (21). This compound is readily hydrolyzed aluminum oxyacid salts be prepared by nonaqueous routes.
and, depending on the temperature, forms the hexahydrate Some of these salts are of particular technological value.
(above 21 C) or a mixture of 2CaOAl2 O3 5 9H2 O and
4CaOAl2 O3 12 14H2 O (below 21 C). 7.1 Aluminum Phosphates
Reaction of AlBr3 with N2 O5 produces white hygroscopic Aluminum perchlorate, Al(ClO4 )3 , is synthesized by treat-
crystals of the salt [NO2 ]+ [Al(NO3 )4 ] . The [Al(NO3 )4 ] ment of AlCl3 with AgClO4 in C6 H6 (equation 30). It is a
anion (22) may also be obtained as the alkali metal or very strong oxidant that reacts slowly with paraffin hydro-
tetraethylammonium salts by the reaction of the appropriate carbons. It decomposes at 150 C and should be considered
nitrate salt, nitric acid, or N2 O5 with AlBr3 . Use of an excess a potential explosive. Aluminum periodate may be obtained
of metal nitrate affords the [Al(NO3 )5 ]2 anion (23). in the same manner. Aluminum iodate, Al(IO3 )3 , is obtained
by thermal decomposition of [Al(OH2 )6 ][IO3 ][HI2 O6 ]HIO3
at 340 C.
O O
N N
O O 3AgClO4 + AlCl3 Al(ClO4 )3 + 3AgCl (30)
O2NO O O2NO O
Al Al
O2NO O O2NO ONO2
O ONO2
N
O 8 THE AQUA IONS AND AQUEOUS CHEMISTRY
(22) (23)
9 ALUMINOSILICATES The structure consists of Te4 Al4 Al4 Te4 units that contain
Al2 Te2 four-membered rings (see Tellurium: Inorganic
Aluminosilicates form an extensive family of compounds Chemistry).
that include layered compounds (such as clays, talc, and
micas), 3-D compounds, (e.g. feldspars, such as granite),
and microporous solids known as molecular sieves.23 The
structural diversity of these materials is contributed to by 11 ALUMINUM PNICTIDES
aluminums ability to occupy both tetrahedral and octahedral
holes as it also does in -Al2 O3 . Thus, aluminum substitution The compounds of group 13 and group 15 have
for silicon in silicate minerals may lead to replacement of achieved considerable technological importance owing to their
silicon in tetrahedral sites or the aluminum can occupy application as III V semiconductors (these compounds are
an octahedral environment external to the silicate lattice. isoelectronic with Si and Ge) (see Compound Semiconductor).
Replacement of SiIV with AlIII requires the presence of an AlN, AlP, AlAs, and AlSb may all be prepared by direct
additional cation such as H+ , Na+ , or 0.5 Ca2+ to balance the combination of the elements at elevated pressures (see
charge. These additional cations have a profound effect on the Pnictide). All have the sphlaerite structure with the exception
properties of the aluminosilicates. This accounts for the many of aluminum nitride, which has the wurtzite structure. The
types of layered and 3-D structures (see Silicon: Inorganic properties of the compounds are given in Table 7 and they
Chemistry).
show the clear trends towards lower-melting point and smaller
The molecular sieves are aluminosilicates of particular
band gap with increasing atomic number of the pnictide (see
importance. They are crystalline materials that have open
also Phosphides: Solid-state Chemistry).
structures that contain pores and channels that have molecular
Aluminum nitride was first synthesized in 1877, but it was
dimensions. This family of materials includes the zeolites,
a relatively unimportant material until mid-1980s when its
which have numerous applications in heterogeneous catalysis,
potential for application in microelectronics was realized. It
ion-exchange materials, absorption of molecular species,
has very high thermal conductivity for a ceramic material
and gas separation. While some zeolites occur naturally,
(320 W/mK) that is second only to beryllium oxide Unlike
they are usually manufactured from silicon and aluminum
BeO, AlN is nontoxic so it became the material of choice
oxides mixed with tetraalkylammonium templates in a high-
for substrates for microelectronic circuits that require rapid
pressure autoclave (see Zeolites).
removal of heat. A high dielectric strength (>20 kV/mm)
and high resistivity (1010 ohmcm) also contribute to the
performance of AlN in these applications. AlN is generally
synthesized by carbothermal reduction of alumina or by direct
10 ALUMINUM CHALCOGENIDES nitridation of aluminium. AlN can also be prepared by reaction
of AlCl3 and NH3 at 1200 C (equation 33).24 Fashioning AlN
Under ordinary conditions, the stable binary chalcogenides into ceramic bodies and substrates is difficult because it does
(Chalcogens) of aluminum are Al2 S3 (white), Al2 Se3 (gray), not have a melting point but dissociates above 2500 C at
and Al2 Te3 (dark gray). Their band gaps are 4.1, 3.1, and atmospheric pressure. The materials strong covalent bonding
2.2 eV, respectively, showing the expected trend to smaller makes it resistant to sintering without the assistance of liquid
band gap (see Band Gap). They are prepared by the direct forming additives. Such additives include oxides like Y2 O3
combination of the elements at 1000 C and must be protected or CaO that allow sintering to be achieved at temperatures
from moisture owing to rapid hydrolysis to Al(OH)3 and between 1600 and 1900 C. As a powder, aluminum nitride
H2 X (X = S, Se, Te) (equation 32). The relatively large size is susceptible to hydrolysis by water or humidity to produce
of the anions with respect to aluminum leads to tetrahedral aluminum hydroxide and ammonia. This is not a problem
coordination of the latter. Therefore, the various polymorphs for ceramic monoliths since the reaction is limited to the
adopt a wurtzite structure with two-thirds of the available surface. Items manufactured from AlN are resistant to attack
metal sites being occupied by aluminum. If this occupation from most molten salts including chlorides and cryolite
is ordered, the modification is called -Al2 X3 ; if not, and most molten metals including aluminium, lithium, and
then the phase is called -Al2 X3 . Al2 S3 also forms a - copper. Unfortunately, aluminum nitride is readily attacked
form similar to -alumina (see Chalcogenides: Solid-state
Chemistry).
Table 7 Some properties of Al III V compounds
Al2 Y3 + 6H2 O 2Al(OH)3 + 3H2 Y (32)
Property AlN AlP AlAs AlSb
(Y = S, Se, Te)
Color Pale/yellow Yellow Orange Black
Mp ( C) >2200 decomp 2000 1740 1060
Al7 Te10 may be prepared by fusion of the elements. Eg (eV) 4.26 2.45 2.16 1.50
It is one of the few compounds with an AlAl bond.
14 ALUMINUM: INORGANIC CHEMISTRY
by acids and alkalis as are most aluminum compounds. a very complex structure. This consists of AlC4 tetrahedra that
Films of AlN can provide useful wear resistance and may are linked to form a layered lattice. There are two types of
be obtained by various chemical vapor deposition methods carbon atoms: one that is surrounded by a distorted octahedron
(see Metal Organic Chemical Vapor Deposition). of aluminum atoms at 217 pm and one that is surrounded by
four aluminum atoms at 190 194 pm and a fifth one at 221 pm.
AlCl3 + 4NH3 AlN + 3NH4 Cl (33) Aluminum carbide hydrolyzes very readily to Al(OH)3 and
methane (equation 36) (see Carbides: Transition Metal Solid-
Aluminum phosphide, like aluminum nitride, reacts with state Chemistry).
moisture but in this case the gaseous product is phosphine,
PH3 , a very toxic gas. For this reason, AlP is used as a fumigant Al4 C3 + 12H2 O 4Al(OH)3 + 3CH4 (36)
to control insects in stored products such as raw agricultural
products, animal feeds, processed foods (for example, flour
and sugar), tobacco, wood, paper, leather, hair, and feathers. There are several aluminum boride phases known.26 One
It is also used for control of rodents such as rats, mice, of the more common, AlB12 , is employed in the manufacture
squirrels, and gophers in and around mills, food processing of lightweight armor, as a catalyst for organic reactions, and
plants, warehouses and silos, and in rail cars, ships, and as a economical replacement for diamond abrasive. It has
shipping containers. a complex structure composed of B12 icosahedra, B19 units
(twinned icosahedra), and single boron atoms in a 2:1:1 ratio.
The aluminum atoms are distributed statistically over all the
boron sites. AlB12 is synthesized by direct combination of the
elements at 1100 C or by reaction of aluminum with Na4 B4 O7
12 MIXED ALUMINUM CHALCOGENIDE
at 1100 C.
HALIDES
AlB2 may be conveniently prepared by reaction of
aluminum with H3 BO3 , KBF4 , or B2 O3 /KCl mixtures at
The reaction of aluminum halides with a variety of oxides at temperatures between 800 and 1300 C. AlB2 is a metallic
elevated temperatures yields the aluminum oxyhalides, AlOX
conductor (conductivity of 333 1 m1 ) that slowly reacts
(equation 34). These compounds are insoluble, moisture-
with water and aqueous hydrochloric acid. The structure
sensitive compounds that have an interesting layered structure.
consists of hexagonal nets of boron atoms with each boron
The aluminum atoms have tetrahedral coordination by three
atom surrounded by six aluminum atoms at the corners of
oxygen atoms and one halide atom. The oxygen atoms of
trigonal prisms.
the tetrahedra are shared between three aluminum atoms,
An aluminum boride that is intermediate between the
providing a puckered AlO layer. The halide atoms cap the
two extremes above, AlB4 , has a structure consisting of
tetrahedra, half of them above and half of them below the AlO
B6 octahedra that are linked by B2 units forming tunnel-
layer in an alternating fashion.25 The hydrate of AlOCl is used
like cavities in which the aluminum atoms lie (see Boron:
as an antiperspirant.
Inorganic Chemistry).
3AlX3 + M2 O3 3AlOX + 2MX3 (34)
(M = As, Bi, Sb; X = Cl, Br, I)
Al4 C3 is prepared by direct union of the elements at elevated 2Al + 6ROH 2Al(OR)3 + 3H2 (37)
temperatures. It forms pale-yellow crystals (mp 2200 C) with Al(OR)3 + 3MeCO2 R Al(OR )3 + 3MeCO2 R (38)
ALUMINUM: INORGANIC CHEMISTRY 15
The alkoxides of aluminum are polymeric with aluminum coordination (28) of aluminum was proposed.
achieving four or six coordination. The adopted structure
depends greatly on the bulkiness of the alkyl groups. For R
sterically large groups, for example, tertiary butyl, the O
preferred structure is a dimer (25). The isopropoxide, on O O
Al(OR)3 + 3RCO2H 3ROH + R Al
the other hand, is trimeric (26) at elevated temperatures but O O
tetrameric (27) at room temperature.27 O
R
(28)
RO OR
R (39)
RO O OR Al
Al Al RO OR
RO OR
RO O OR Al Al The tricarboxylates are highly susceptible to hydrolysis, are
R O
RO R OR nonvolatile, and thermally unstable. They lose one equivalent
of acid anhydride upon heating to 200 C to form carboxy-
substituted alumoxanes, (RCO2 AlO)n . The latter compounds
(25) (26) have been used as precursors for alumina fibers and films and
are more conveniently prepared from the mixed aluminum
alkoxide monocarboxylate (equation 40).
OR
Al OR Al(OR)2 (O2 CR ) + H2 O ROH + Al(OR)(OH)(O2 CR )
RO R RO ROH + [OAl(O2 CR )]n (40)
O OR
Al Al
O
RO R RO OR
Al OR
OR 16 RELATED ARTICLES
(27)
Boron: Inorganic Chemistry; Fluorides: Solid-state Chem-
istry; Gallium: Inorganic Chemistry; Halides: Solid-state
The siloxides of aluminum can be prepared in the same Chemistry; Indium: Inorganic Chemistry; Oxide Catalysts
manner as the alkoxides and exhibit similar structural features. in Solid-state Chemistry; Oxygen: Inorganic Chemistry;
Interest in these compounds arose from a desire for sol gel Phosphates: Solid-state Chemistry; Phosphides: Solid-state
or polymeric precursors for aluminosilicates. Unfortunately, Chemistry; Silicon: Inorganic Chemistry; Sol Gel Synthesis
these compounds extensively hydrolyze, losing most of of Solids; Tellurium: Inorganic Chemistry; Zeolites.
the silicon as the silanol. However, the investigation of
the hydrolysis of (Et3 SiO)3 Al has generated considerable
insight into the structure and composition of alkoxy- and
siloxy-substituted alumoxane polymers, (ROAIO)n .28 These 17 FURTHER READING
macromolecules are now believed to have a structure related
to that of boehmite.
J. W. Akitt, in Multinuclear NMR, ed. J. Mason, Plenum, New
York, 1987, Chap. 9, p. 259.
C. J. Brinker and G. W. Scherer, Sol Gel Science, Academic Press,
San Diego, CA, 1990.
15 ALUMINUM CARBOXYLATES
A. K. Vasudevan and R. D. Doherty, in Aluminum Alloys Con-
temporary Research and Applications, eds. A. K. Vasudevan and
Aluminum carboxylates have been extensively investigated R. D. Doherty, Academic Press, Boston, 1989.
because of their applications as textile finishing, gelling, and
therapeutic agents. Despite this, the structural aspects of their
chemistry are not well established.29
Aluminum tricarboxylates may be synthesized by methods 18 REFERENCES
analogous to those employed for the alkoxides. However,
they are best obtained by the reaction of the alkoxides with 1. D. L. Hart ed., Aluminum Chemicals Science and Technology
carboxylic acids (equation 39). The tricarboxylates have been Handbook, American Ceramic Society, Washington, DC,
demonstrated to be monomeric in benzene and octahedral 1990.
16 ALUMINUM: INORGANIC CHEMISTRY
2. W. C. Sleppy, Kirk Othmer Encyclopedia of Chemical 15. J. T. Kummer, Prog. Solid State Chem., 1972, 7, 141.
Technology, 5th edn., Wiley, New York, 2004, Vol. 2. 16. J. H. Kennedy, Top. Appl. Phys., 1977, 21, 105.
3. H. L. Hurlburt, in Encyclopedia of Chemical Processing and 17. M. G. Parker, P. G. Gadd, and M. J. Begley, J. Chem. Soc.,
Design, eds. J. J. McKetta and W. A. Cunningham, Marcel Chem. Commun., 1981, 379.
Dekker, New York, 1977, Vol. 3.
18. M. G. Parker, P. G. Gadd, and S. C. Wallwork, J. Chem. Soc.,
4. E. Wiberg and E. Anberger, Hydrides of the Elements of Main Chem. Commun., 1982, 516.
Groups I IV, Elsevier, Amsterdam, 1971.
19. J. H. Morris, P. G. Perkins, A. E. A. Rose, and W. E. Smith,
5. A. E. Finhold, A. C. Bond, and H. L. Shlesinger, J. Am. Chem. Chem. Soc. Rev., 1977, 6, 173.
Soc., 1947, 69, 1199.
20. J. M. Bennett, W. J. Dytrych, J. J. Pluth, J. W. Richardson, and
6. N. G. Gaylord, Reduction with Complex Metal Hydrides, J. V. Smith, Zeolites, 1986, 6, 349.
Interscience, New York, 1956.
21. S. T. Wilson, B. M. Lok, C. A. Messina, T. R. Cannan, and
7. A. R. Barron and G. Wilkinson, Polyhedron, 1986, 5, E. M. Flanigan, J. Am. Chem. Soc., 1982, 104, 1146.
1897.
22. C. F. Baes and R. E. Mesmer, The Hydrolysis of Cations,
8. F. L. Himpsl and A. C. Bond, J. Am. Chem. Soc., 1981, 103, Wiley, New York, 1976.
1098.
23. F. Liebav, Structural Chemistry of the Silicates, Springer-
9. A. F. Wells, Structural Inorganic Chemistry, 4th edn., Oxford Verlag, New York, 1985.
University Press, Oxford, 1975.
24. D. D. Marchant and T. E. Nemecek, Adv. Ceram., 1989, 26, 19.
10. N. N. Greenwood and K. Wade, in Friedel Crafts and Related
25. S. S. Batsanov and V. N. Kolomiichuk, J. Struct. Chem. USSR,
Reactions, ed. G. A. Olah, Interscience, New York, 1963, Vol.
1968, 9, 282.
1, Chap. 7, p. 569.
26. N. N. Greenwood, R. V. Parish, and P. Thornton, Q. Rev. Chem.
11. C. L. Hussey, Adv. Molten Salt Chem., 1983, 5, 185.
Soc., 1966, 20, 441.
12. C. Misra, Industrial Alumina Chemicals, American Chemical
27. D. C. Bradley, R. C. Mehrotra, and D. P. Gaur, Metal
Society, Washington, DC, 1986.
Alkoxides, Academic Press, London, 1978.
13. N. N. Greenwood, Ionic Crystals, Lattice Defects, and
28. A. Barron and A. Apblett, Chem. Mater., 1992, 69, 167.
Nonstoichiometry, Butterworths, London, 1968.
29. R. C. Mehrotra and R. Bohra, Metal Carboxylates, Academic
14. J. K. Burdett, G. D. Price, and S. L. Price, J. Am. Chem. Soc.,
Press, London, 1983.
1982, 104, 92.
Aluminum: organomagnesium reagents. This perception and the status
of organoaluminum compounds changed suddenly with the
pioneering work of Karl Ziegler in 1949.5 Ziegler discovered
Organometallic Chemistry that base-free alkylaluminum compounds could be synthesized
on large scale by direct synthesis from aluminum, hydrogen,
Mark R. Mason and alkenes. He also showed that these organoaluminum
University of Toledo, Toledo, OH, USA compounds react with ethylene to give long-chain terminal
alkenes and alcohols, products that are still used today
Based in part on the article Aluminum: Organometallic Chemistry for the production of surfactants and detergents. In 1953,
by Gregory H. Robinson which appeared in the Encyclopedia of Ziegler applied for his first patent on the polymerization of
Inorganic Chemistry, First Edition. ethylene under mild conditions using a catalyst comprised of a
trialkylaluminum compound and an early transition metal such
1 Introduction 1 as titanium and zirconium. Karl Ziegler shared the 1963 Nobel
2 Aluminum(III) Alkyls, Aryls, Hydrides, and Prize in Chemistry with Giulio Natta for his contribution to
Halides 1 Ziegler Natta alkene polymerization catalysis.
3 Low-valent Organoaluminum Compounds 9 During the same period, Edwin Vandenberg and his
4 Organoaluminum Heterocycles and Cage colleagues at Hercules were independently working on
Compounds 11 Ziegler-type catalysts for the polymerization of propylene
5 Cationic Organoaluminum Compounds 17 and polar monomers. As part of this effort, the use of
6 Anionic Organoaluminum Compounds 19 an old bottle of wet epichlorohydrin led Vandenberg to
7 Applications of Organoaluminum Compounds in serendipitously discover that partially hydrolyzed aluminum
Synthesis 20
alkyls are active catalysts for the ring-opening polymerization
8 Applications of Organoaluminum Compounds in
Industry 20
of epoxides and oxetanes.6 Vandenberg catalysts composed
9 Safety Considerations 22
of a partially-hydrolzed aluminum alkyl, acetylacetonate, and
10 Related Articles 22
various proprietary additives led to the commercial production
11 References 22 of polyether elastomers that are still of significant industrial
importance today. For his contributions to polymerization
catalysis using organoaluminum reagents, Ed Vandenberg
was awarded the Priestley Medal, the highest honor bestowed
Glossary by the American Chemical Society, in 2003.
The discoveries of Ziegler, Vandenberg, and many others
Aluminum alkyl: compounds of aluminum in which a bond in the 1950s and 1960s ushered in the modern age
exists between aluminum and a carbon of an alkyl group of organometallic chemistry of aluminum and a host of
applications followed. By 1967, U.S. production capacity for
organoaluminum compounds was estimated at 50 60 million
lb/year. The importance of aluminum alkyls continues to rise
to this day as organoaluminum compounds are used in organic
1 INTRODUCTION synthesis, catalysis, and the preparation of new materials.
This contribution provides a summary of basic principles
Aluminum is the most abundant metal and the third most of the organometallic chemistry of aluminum and emphasizes
abundant element in the Earths crust, behind only oxygen and new developments since publication of the first edition of the
silicon. Its low weight and useful properties make aluminum Encyclopedia of Inorganic Chemistry. References are intended
and its alloys valuable materials for manufacturing and to guide readers to detailed reviews covering all aspects of the
electrical applications. Inorganic compounds of aluminum are organometallic chemistry of aluminum. In particular, readers
plentiful and used as absorbents, catalysts, ionic conductors, should consult the classic work of Mole and Jeffery7 and
ceramics, and electrical materials. Organometallic compounds reviews by Eisch8,9 and Robinson.10,11
of aluminum are also of great industrial importance and
fundamental discoveries continue to be made regarding the
variety of coordination numbers, structures, oxidation states,
and reactivity exhibited by aluminum.14 2 ALUMINUM(III) ALKYLS, ARYLS, HYDRIDES,
The preparation of the first organoaluminum compound, AND HALIDES
Et3 Al2 I3 , was reported by Hallwachs and Schafarik in
1859, but the utility of organoaluminum reagents was
2.1 Preparative Routes
not realized for nearly a hundred years. This was likely
due to the misconception that organoaluminum compounds Four methods are used for the industrial production of
were less reactive than the better-studied organozinc and simple aluminum alkyls: direct synthesis, the displacement
2 ALUMINUM: ORGANOMETALLIC CHEMISTRY
reaction, the growth reaction, and reduction of alkylaluminum preparation of Et3 Al, but direct synthesis is preferred because
sesquihalides.7 In the direct synthesis developed by Ziegler, of the expense of the reducing agent. This method has limited
aluminum alkyls are prepared by reaction of aluminum metal, utility for higher alkyls owing to competitive Lewis acid-
hydrogen, and a terminal alkene (equation 1). The reaction catalyzed elimination of HX from the alkyl halide. It is
worth noting that Hallwachs and Schafarik prepared the
3
Al + H2 + 3RR C=CH2 (RR CHCH2 )3 Al (1) first organoaluminum compound, Et3 Al2 I3 , by reaction of
2
aluminum with iodoethane.
proceeds by formation of a dialkylaluminum hydride followed Additional synthetic protocols are available for the
by insertion of an alkene into the AlH bond. The insertion preparation of research quantities of aluminum alkyls that
of a substituted alkene proceeds in a Markovnikov fashion are not commercially available by the above routes. Of these,
with the hydride transferred to the most substituted carbon reaction of an organomercury reagent with aluminum metal
atom of the double bond. For this reason, the use of
2Al + 3R2 Hg 2R3 Al + 3Hg (9)
propene or isobutene yields tri-n-propylaluminum or tri-iso-
butylaluminum, respectively. Tri-iso-propylaluminum and
tri-tert-butylaluminum cannot be prepared by direct synthesis. (equation 9) is the oldest and of general utility. However,
In the case of ethylene, additional insertions occur to give owing to the toxicity of organomercury compounds (see
mixtures of long-chain trialkylaluminum compounds via the Mercury: Organometallic Chemistry) and environmental
Auf bau, or growth, reaction (equation 2). The resulting concerns, the use of organomercury reagents has been
widely supplanted by reactions of aluminum halides
R3 Al + 3nH2 C=CH2 {R(CH2 CH2 )n }3 Al (2) with organolithium or Grignard reagents according to
equations (10) and (11), respectively.
aluminum alkyls are useful for the commercial production of AlX3 + 3RLi R3 Al + 3LiX (10)
long-chain terminal alkenes and alcohols, but pure aluminum
AlX3 + 3RMgX R3 Al + 3MgX2 (11)
alkyls are not typically prepared in this manner. This is a
convenient route for the preparation of research quantities of
trineohexylaluminum and trineopentylaluminum according to Reaction of anhydrous aluminum trichloride with an
equations (3) and (4). organolithium compound is convenient for preparation of
base-free aluminum alkyls such as i Pr3 Al,12 t Bu3 Al,12
t
Bu3 Al + 3H2 C=CH2 (t BuCH2 CH2 )3 Al (3) (t BuCH2 )3 Al,13 and {(Me3 Si)2 CH}3 Al.14 In contrast, the
use of Grignard reagents often results in the isolation
Me3 Al + 3Me2 C=CH2 (Me3 CCH2 )3 Al (4)
of Lewis acid-base complexes R3 AlL (L = THF, ether)
rather than the more Lewis acidic R3 Al. An exception
In the displacement reaction, reversible -hydride elimi- is the synthesis of tri-tert-amylaluminum from AlCl3 and
nation of an alkene from an aluminum alkyl (equation 5) is (Me2 EtC)MgCl in diethyl ether and hexane.15 The ether adduct
followed by insertion of a different alkene into the AlH bond (Me2 EtC)3 AlOEt2 is not isolated, presumably owing to the
of the resulting dialkylaluminum hydride (equation 6). Three steric congestion at aluminum based on comparison of the
repetitions of this process yield the new trialkylaluminum estimated Tolman cone angle16 for the tert-amyl substituent
compound as in equation (7). Tri-iso-butylaluminum obtained (135 140 ) with that for tert-butyl (126 ) and isopropyl (114 )
from the direct synthesis is a convenient starting aluminum substituents.
alkyl for this process. Organoaluminum halides are most conveniently prepared
by redistribution reactions. Mixing a trialkylaluminum and
an aluminum halide in a 1:1, 2:1, or 1:2 ratio yields
i
Bu3 Al i
Bu2 AlH + Me2 C=CH2 (5)
bis halide-bridged compounds R3 Al2 X3 , R2 AlX, or RAlX2 ,
i
Bu2 AlH + RR C=CH2 i
Bu2 AlCH2 CHRR (6) respectively. Alternative routes include reactions of aluminum
i
Bu3 Al + 3RR C=CH2
(RR CHCH2 )3 Al + 3Me2 C=CH2 (7) halides with organolithium or Grignard reagents in the desired
stoichiometry and reaction of trialkylaluminum compounds
Trimethylaluminum cannot be prepared by any of the above with halogen to give the organoaluminum halide and alkyl
processes, which rely on alkene insertion. The industrial halide. Reactions of alkyl halides with aluminum metal
preparation of trimethylaluminum is achieved by reaction can also be used to prepare organoaluminum halides as
of ground aluminum with chloromethane to yield the previously mentioned.
sesquichloride, Me3 Al2 Cl3 , and subsequent reduction with The preparation of organoaluminum fluorides differs
sodium metal (equation 8). This procedure also works for the somewhat from that of other organoaluminum halides.17
Redistribution reactions using AlF3 do not work well, nor do
6MeCl 6Na
reactions of AlF3 with Grignards or organolithium reagents.
4Al 2Me3 Al2 Cl3 2Me3 Al + 2Al + 6NaCl (8) Organoaluminum fluorides are best prepared by salt metathesis
ALUMINUM: ORGANOMETALLIC CHEMISTRY 3
upon mixing R2 AlX or RAlX2 with sodium fluoride. Exchange prepared by reaction of Cp2 Hg with aluminum and by reaction
reactions with BF3 and reactions of a trialkylaluminum with of AlCl3 with magnesocene (equation 18). Magnesocene
HF also work well as shown in equations (12) and (13).
3Cp2 Mg + 2AlCl3 3MgCl2 + 2Cp3 Al (18)
3R3 Al + BF3 3R2 AlF + R3 B (12)
R3 Al + 2HF RAlF2 + 2RH (13) derivatives are very effective for preparing cyclopentadi-
enylaluminum compounds such as (C5 MeH4 )3 Al, (1,2,4-
C5 Me3 H2 )3 Al, and (C5 Me4 H)3 Al. Incomplete exchange
Organoaluminum halides can be used to prepare pseu-
occurs upon reaction of (C5 Me5 )2 Mg with AlCl3 and
dohalide derivatives, such as azides18 and cyanides, by salt
Cp AlCl2 is obtained. Cyclopentadienyl aluminum com-
metathesis. Azides are prepared by trimethylsilylhalide elim-
pounds are often prepared by salt metathesis reactions of
ination (equation 14) and by reaction of a trialkylaluminum
AlCl3 or an organoaluminum halide with a CpM deriva-
with chloroazide, ClN3 . Organoaluminum cyanides have also
tive (M = Li, Na, K, Tl), but again, exchange is not always
been prepared by reactions of a trialkylaluminum with HCN
complete and cyclopentadienylaluminum halides are some-
(equation 15).7
times obtained. Cyclopentadienylaluminum compounds have
also been prepared by trimethylsilylchloride elimination and
R2 AlX + Me3 SiN3 R2 AlN3 + Me3 SiX (14)
alkane elimination reactions, but these preparative routes are
R3 Al + HCN R2 AlCN + RH (15) less common. Redistribution reactions can occur as in the
conversion of Cp2 AlMe to Cp3 Al and CpAlMe2 .
Several methods exist for the preparation of organoalu- Jordan and coworkers have recently prepared several ansa-
minum hydrides R2 AlH and RAlH2 .7,19 Organoaluminum bis(indenyl) compounds {(AlMe2 L)indenyl}2 SiMe2 and 1,2-
hydrides are obtained by alkene elimination upon heat- {(AlMe2 L)indenyl}2 C2 H4 (L = THF, Et2 O, 1,4-dioxane) by
ing trialkylaluminum compounds that possess a -hydrogen a salt metathesis route.26 These were reacted with M(NMe2 )4
(equation 5). Hydrogenolysis of AlC bonds can be used to (M = Zr, Hf ) to eliminate [Me2 AlNMe2 ]2 and form ansa-
form hydrides (equation 16), but high temperatures and pres- metallocene complexes of bis(dimethylamido)zirconium and
sures are required in the absence of a transition metal catalyst. bis(dimethylamido)hafnium. A simple tris(indenyl)aluminum
Ligand redistribution reactions and reduction of organoalu- compound has been prepared by reaction of bis(indenyl)mer-
minum halides with metal hydrides are also employed. cury with aluminum metal.7
Similar to aluminum alkyls, aluminum aryls are pre-
pared from organomercury, organomagnesium, organo-
120 C
Et3 Al + H2 Et2 AlH + CH3 CH3 (16) lithium, organoborane, or organotin reagents. Triphenylalu-
300 atm
minum and substituted derivatives can be prepared by several
of these methods. Halide derivatives such as Ph2 AlCl and
Several of the trialkylaluminum and alkylaluminum halides PhAlCl2 are prepared by ligand redistribution upon reaction
and hydrides mentioned above are commercially available. of Ph3 Al with AlCl3 .
Alkynyl, alkenyl, cyclopentadienyl, and aryl derivatives are, Monomeric trimesitylaluminum is prepared from Mes2 Hg
in general, not commercially available and must be synthesized and aluminum,27 or by removing THF or ether from Mes3 AlL
for laboratory use. Alkynyl derivatives can be prepared by salt (L = THF, OEt2 ) with heating in vacuo.28 Mesityl derivatives
metathesis, as in the reaction of Et2 AlCl with NaCCEt Mes2 MeAlTHF, Mes2 EtAlTHF, and Mes2 ClAlTHF were
to give Et2 AlCCEt.20 The acidity of terminal alkynes is prepared by reactions of MesMgBr with MeAlCl2 , EtAlCl2 ,
sufficient for preparation of alkynyl aluminum compounds and AlCl3 , respectively,29 and the chloro-bridged dimer
by alkane or hydrogen elimination upon reaction with a [Mes2 AlCl]2 has been prepared by ligand redistribution.
trialkylaluminum or an aluminum hydride (equation 17), Tris(pentamethylphenyl)aluminum is obtained base-free by
respectively.21 Trialkynyl aluminum compounds are typically reaction of AlCl3 with C6 Me5 MgBr in diethyl ether.30 The
isolated as Lewis base adducts to stabilize them against isolation of the base-free alane is in contrast to the formation
otherwise facile polymerization. Alkenyl compounds of of Mes3 AlL by the Grignard route.
aluminum have similarly been prepared. There are fewer preparative methods for m-terphenyl
derivatives of aluminum.31 Aluminum bromide reacts
3H2 with [2,4,6-Ph3 C6 H2 Li]2 to give 2,4,6-Ph3 C6 H2 AlBr2 OEt2 ,
H3 Al(NMe3 ) + 3HCCPh (PhCC)3 Al(NMe3 ) (17)
but analogous procedures do not give the corre-
sponding dichlorides. Alternatively, reaction of [2,6-
Cyclopentadienyl compounds of aluminum have been Mes2 C6 H3 Li]2 with AlH3 NMe3 in ether, followed by reaction
increasing studied over the past decade.2225 They are with chlorotrimethylsilane yields (2,6-Mes2 C6 H3 )AlH2 OEt2 .
prepared using the same methods used for simple aluminum Ether can be removed in vacuo and additional treatment with
alkyls. Tris(cyclopentadienyl)aluminum, for example, can be chlorotrimethylsilane yields the organoaluminum dichloride
4 ALUMINUM: ORGANOMETALLIC CHEMISTRY
structural data for organoaluminum compounds.48 There is Much of the reaction chemistry of aluminum trialkyls can
also a compilation of 727 organoaluminum compounds with be classified by the following reaction types, some of which
references to the synthesis and spectroscopic and structural are illustrated in Scheme 1: oxidation, alkane elimination
characterization of each compound.49 in the presence of protic reagents, AlC bond cleavage
via halogenation and hydrogenation, insertion reactions,
-hydrogen elimination (equation 5), and coordination of
2.3 Reactivity Lewis bases.
Protic reagents such as water, alcohols, acids, and primary
Neat aluminum trialkyls are highly reactive, colorless
and secondary amines react rapidly with aluminum alkyls
liquids that spontaneously ignite in the presence of oxygen,
resulting in alkane elimination and coordination of the
react violently with water, and must be manipulated
conjugate base of the protic reagent. Reagents must be
and stored under an inert atmosphere. Trialkylaluminum
added slowly to avoid dangerous exothermic reaction and
compounds react vigorously with halogenated solvents and
gas evolution, particularly for Me3 Al and Et3 Al. Subsequent
even react with silicone stopcock grease50 with cleavage of
reactivity of the AlC bonds decreases as more alkyl groups
SiO and formation of AlO bonds. Reactivity is greatest
are removed, and vigorous conditions are often required to
for trimethylaluminum (37.4 wt% Al) and decreases with
decreasing weight percent of aluminum. Handling aluminum remove the last aluminum alkyl. Reaction of Me3 Al with
alkyls as dilute solutions in inert hydrocarbons reduces the alcohol rapidly forms Me2 AlOR followed by formation of
risk of ignition. Tri-iso-butylaluminum is typically available MeAl(OR )2 , but the last methyl group in MeAl(OR )2 reacts
as a 25-wt% solution in toluene. Bulky alkyl and aryl with alcohols reluctantly.
groups moderate the reactivity. Aluminum triaryls are white Insertion reactions are commonplace for organoaluminum
solids that fume in air, but oxidize more slowly than do compounds. Insertion of oxygen into the AlC bonds of
aluminum trialkyls. alumium trialkyls proceeds cleanly at low temperatures in
The reactivity of organoaluminum compounds is attributed hydrocarbon solvents to give aluminum alkoxides. The first
to their low thermodynamic stability and high kinetic lability. insertion is rapid, as usually is the second. The third insertion
The mean bond enthalpy for the AlC bond in Me3 Al is is considerably slower depending on the steric bulk of the
274 kJ mol1 (Table 1).51 This is less than the EC bond resulting alkoxide complexes. Oxygen insertion is believed
enthalpies for E = boron, carbon, nitrogen, and silicon and to proceed via an alkylperoxy intermediate R2 AlOOR by
only 55 and 65% of the AlO and AlCl bond enthalpies, analogy to the structurally characterized gallium and indium
respectively. There is clearly a strong thermodynamic driving alkylperoxides [t Bu2 MOOt Bu]2 (M = Ga, In).52 Lewinski
force for oxidation and hydrolysis. Enthalpies of combustion and coworkers have structurally characterized an alkylperox-
and hydrolysis for Et3 Al, for example, are 5104 and ide complex of aluminum (11) isolated after O2 insertion into
527 kJ mol1 , respectively.7 Although AlC bonds may be the AlC bonds of t Bu2 Al(methylsalicylate).53,54 Complex
considered weak based on mean bond enthalpies, they are
comparable in strength to PC bonds, which are considerably
R2AlOR
less reactive than AlC bonds in aluminum trialkyls. Thus, the
RAl(OR)2
reactivity of organoaluminum compounds is equally related
Al(OR)3
to their kinetic lability. This lability is due to the availability
of a low-lying acceptor orbital in three-coordinate monomeric Al(O2SR)3 R2AlH
trialkylaluminum compounds and potential participation of O2
empty d orbitals. Furthermore, the AlC bond is highly
SO
2
2
CO2 X2
the Pauling electronegativity of aluminum (1.6) and carbon
R2AlO2CR R3Al R2AlX
(2.5) is greater than for any other MC bond of a p-block X = Cl, Br, I
RR
Li
H
HX
R
Al (1.6).
R2AlCH2CHRR Li[AlR4]
Table 1 Selected mean bond dissociation enthalpies (kJ mol1 ) for R2AlX
p-block elements RAlX2
AlX3
BC 365 CC 358
AlC 274 SiC 311 X = F, Cl, Br, I, OR, SR, NR2
GaC 247 GeC 249
AlO 500 NC 314
AlCl 420 PC 276 Scheme 1 Representative reactions of trialkylaluminum
compounds
8 ALUMINUM: ORGANOMETALLIC CHEMISTRY
tBu
MeO
O (12)
tBu
O
O
O O tBu
Al Al
O O
O tBu C O tBu
tBu O
t Al Al
Bu tBu tBu
MeO O C
tBu
(11)
(13)
aluminum analog of an alkene (see Main Group: Multiple and -acceptor potential. The Cp Al moiety functions as a
Bonding). The dianion, however, remains elusive. A one- ligand towards main group and transition metals to form com-
electron reduction of R2 AlAlR2 to form [R2 AlAlR2 ] plexes such as Cp Al B(C6 F5 )3 (18), Cp Al Al(C6 F5 )3 ,
has been successful for both 2,4,6-triisopropylphenyl and Cp Al Cr(CO)5 , and Cp Al Fe(CO)4 . The only hexam-
bis(trimethylsilyl)methyl substituents.67 Reduction leads eric organoaluminum(I) cluster containing AlAl bonds is
[Al6 t Bu6 ] (19).
to a planar Al2 C4 core structure and a decrease in
the AlAl bond distance by 6 7%, from 2.660(1) A
in {(Me3 Si)2 CH}2 AlAl{CH(SiMe3 )2 }2 to 2.53(1) A in
[{(Me3 Si)2 CH}2 AlAl{CH(SiMe3 )2 }2 ] and from 2.647(3) A
in R2 AlAlR2 to 2.470(2) A in [R2 AlAlR2 ] (R = 2,4,6-
i
Pr3 C6 H2 ). The decrease in AlAl distance upon reduction
is consistent with increased bond order. Power has simi- Al
larly attempted to reduce I(R)AlAl(R)I with two equivalents
of potassium to give the dialuminene species RAl=AlR Al Al
(R = 2,6-i Pr2 C6 H3 ).68 The desired compound was not iso- Al
lated, but its formation was indicated by isolation of a
cycloaddition product with toluene.
In 1991, Uhl reported that reduction of i Bu2 AlCl with
potassium in hexanes yielded K2 [Al12 i Bu12 ] (Figure 1).
The AlAl distances in [Al12 i Bu12 ]2 average 2.660 A,
(17)
comparable to that in {(Me3 Si)2 CH}2 AlAl{CH(SiMe3 )2 }2 .
Despite the extensive chemistry of icosahedral boranes (see
Boron: Polyhedral Carboranes), this is the first analog of
an icosahedral borane for the heavier group 13 elements.
Aluminum has been incorporated into polyhedral boranes and
carboranes. Polyhedral carbaalanes have also been prepared
Al
and recent developments in this area have been reviewed.69
Also in 1991, Schnockel65,66 reported that reaction of AlCl B
with Cp2 Mg yielded [Cp Al]4 (17). This can also be synthe- F5
sized by reaction of [Cp AlX2 ]2 with Na/K alloy. Substituted- F5
cyclopentadienyl and silyl derivatives of aluminum(I) have
similarly been prepared.23,24 The AlAl bonds in [Cp Al]4 F5
(average 2.769 A) are longer than those in the dialanes and (18)
may be cleaved thermally to give monomeric Cp Al in the
gas phase. The AlAl bonds in [Cp Al]4 insert selenium
and tellurium to give the chalcogenide cubanes [Cp AlE]4 tBu
(19)
215 C
7Me3 Al + 7MeNH2 [MeAlNMe]7 (26)
14CH4
[RAlNR]4 [RAlNR]6
complex Me3 AlNH2 Me, and heating this complex to 70 C
yields cis and trans isomers of the cyclic aminoalane
[Me2 AlNHMe]3 . Continued heating to 215 C results
in further methane elimination and formation of the
heptameric iminoalane, [MeAlNMe]7 , via intermediate
[(Me2 AlNHMe)2 (MeAlNMe)6 ] (23).
[RAlNR]7 [RAlNR]8
Me Me Me
Me Me
H Me Me
Figure 2 Core structures for organoiminoalanes with nitrogen and
Me Me aluminum atoms alternating at cage vertices. Organic substituents R
Me
Me and R are omitted for clarity
Me H
Me Me
Me Me Me
(23) shorter than those between the six-membered rings
(1.951(6) A).
In the absence of crystallographic data, mass spectrometry
This reaction sequence is quite general. Primary amines has been used to verify the extent of oligomerization for several
react with trialkylaluminum compounds to form Lewis acid- iminoalanes. Cryoscopic molecular weight measurements
base adducts R3 AlNH2 R , followed by alkane elimination to were less reliable. NMR (1 H, 13 C) spectroscopy is also quite
form cyclic dimers and trimers of the formula [R2 AlNHR ]n useful because the symmetries of these cage compounds
(n = 2, 3). Further alkane eliminates from the dimers and differ. Substituents on aluminum will give rise to a single
trimers at higher temperature to afford oligomeric iminoalanes set of resonance in tetramers, hexamers, and octamers of a
[RAlNR ]n . The degree of association for iminoalanes ranges drum-like structure. In contrast, aluminum substituents in an
from 3 to 16 and structurally characterized examples exist octamer of the type shown in Figure 2 give rise to two sets
for a trimer (n = 3), tetramers (n = 4), hexamers (n = 6), of resonances in a 1:1 ratio, and aluminum substituents in a
heptamers (n = 7), and octamers (n = 8). Structures of some heptamer give rise to three sets of resonances in a 3:3:1 ratio.
of the larger oligomers, such as [HAlNi Pr]10 , [HAlNEt]15 , Of course, the same distinctions hold true for the substituents
and [HAlNEt]16 are not known. Each of the known on nitrogen.
structures (Figure 2) is composed of four- and six-membered The degree of association of iminoalanes is dependent on
rings of alternating aluminum and nitrogen atoms. The reaction conditions as well as on the steric requirements of the
tetrahedral aluminum atoms are coordinated by three 3 -NR substituents on aluminum and nitrogen. Smaller substituents
groups. allow the formation of larger cages as in [MeAlNMe]8 ,
Tetramers adopt the familiar cubane structure and hex- whereas sterically demanding substituents favor tetramer
amers adopt a drum-like structure as found in some main formation as observed for [MeAlNMes]4 . The steric bulk
group metal alkoxides. The heptamer may be described as of the 2,6-diisopropylphenyl substituent on nitrogen results in
the fusion of two partial cubanes, one of which is missing formation of the trimeric iminoalane [MeAlN(2,6-i Pr2 C6 H3 )]3
an aluminum atom and the other which is missing a nitro- as shown in equation (27).76 This trimer is unusual in
gen atom. The octamer appears to result from the fusion that it contains both three-coordinate aluminum atoms and
of two Al4 N4 cubanes, each opened along an edge prior to adjacent three-coordinate nitrogen atoms in a planar Al3 N3
their linkage. Structurally characterized examples of cage imi- ring. The AlN distance of 1.782(4) A is very short by
noalanes include the following: [HAlNi Pr]4 , [MeAlNi Pr]4 , comparison with other oligomeric iminoalanes (average
[MeAlNMes]4 , [i BuAlNSiPh3 ]4 , [PhAlNPh]4 , [HAlNi Pr]6 , AlN of 1.92 A) and the normal range of AlN distances
[HAlNn Pr]6 , [MeAlNPh]6 , [MeAlNMe]7 , [EtAlNMe]7 and (1.85 2.00 A). This suggests the presence of N Al -
[HAlNEt]8 . In all of these examples, AlN distances donation and has prompted reference to this trimer as
average approximately 1.92 A, albeit with some minor alumazine by analogy to borazine. Although there are six
variations. For example, the AlN distances in the six- nitrogen lone-pair electrons available for delocalized -
membered rings of [MeAlNPh]6 (1.912(6) A) are slightly bonding, no ring current suggesting aromaticity was observed
ALUMINUM: ORGANOMETALLIC CHEMISTRY 13
Al
tBu
O tBu
Al Al tBu
tBu tBu tBu
O
tBu
Al tBu
Al O O
t
Bu tBu tBu tBu
Al Al
(31)
t O O tBu
Bu
Al
tBu tBu
tBu
tBu
O Al
Al
O
O Al
Al O
tBu
tBu
O t
Bu
Al
Al O tBu (34)
t
Bu
(32)
Homogeneous Catalysis).33,8688 MAO is synthesized by
careful hydrolysis of trimethylaluminum by one of a variety of
tBu tBu patented procedures that vary in the mode of water delivery,
AlO tBu
Al including the use of water-saturated nitrogen vapor, water
O O emulsions in organic solvents, ice, molecular sieves, and
Al
O t Al O various hydrates such as Al2 (SO4 )3 18H2 O, MgCl2 6H2 O,
Al Bu Al tBu
tBu CuSO4 5H2 O, and FeSO4 7H2 O. Nonhydrolytic routes have
Al
O Al O also been described. The method of synthesis has a dramatic
tBu O O influence on the catalytic activity of the resulting MAO.
Al
tBu
Changes in compositions and structures of aluminoxane
(33) products as a function of reaction conditions were detailed
in studies of the hydrolysis of t Bu3 Al.
The structure of MAO remains enigmatic. NMR and IR
structures are analogous to those adopted by some alkali metal spectroscopy, cryoscopic molecular weight measurements,
alkoxides, organogallium sulfides, and organoiminoalanes. mass spectrometry, gel-permeation chromatography (GPC),
Barron proposed that aluminoxanes with cage structures are and computational methods have been used to probe the
strong Lewis acids despite the aluminum atoms being four- structure of MAO, but compositions and structures of
coordinate.83 The cages possess a latent Lewis acidity, which is components remains elusive. No neutral methylaluminoxanes
defined as proclivity of the cage to dissociate one or more AlO have been characterized by X-ray crystallography. Atwood
bonds to form highly Lewis acidic three-coordinate aluminum has characterized the anionic aluminoxanes K[Al7 O6 Me16 ]
centers. The driving force is proposed to be the relief of (35) and [Me4 As]2 [Me2 AlOAlMe3 ]2 .10,11
ring-strain in the cage structure. Hessen and coworkers have
provided reactivity data for a boraluminoxane in support of the
proposed latent Lewis acidity in cage alkylaluminoxanes.84 Me
Me Me
Tetrameric cage compounds with cubane structures have Me O Me
not been isolated. Tetramer formation is observed for Al Al
Me Me
[Mes AlO]4 (34) in which the aluminum atoms remain three- K Me O O
coordinate and cage formation is precluded by the steric bulk Al Al Al Me
of the Mes substituents.85 Compound (34) was prepared by O O Me O
Al Al Me
reaction of [Mes AlH2 ]2 with [Me2 SiO]3 and was not obtained Me
by hydrolysis. Me Me Me Me
Methylaluminoxane (MAO), sometimes referred to as (35)
polymethylaluminoxane (PMAO), currently garners the most
industrial interest of all the alkylaluminoxanes owing to
its activity as a cocatalyst for metallocene-catalyzed alkene In contrast to investigations of aluminoxanes bearing bulky
polymerization (see Oligomerization & Polymerization by t
Bu, Mes, Mes , and CH(SiMe3 )2 substituents, the study of
ALUMINUM: ORGANOMETALLIC CHEMISTRY 15
H3 PO4 with t Bu3 Al to give [R2 AlO2 P(OH)2 R ]2 , followed by This decamer rearranges to a mixture of tetramer and hex-
derivatization with Me3 SiNMe2 , gave complicated mixtures amer in CDCl3 over several days. In another example,
that contained [t Bu2 AlO2 P(OSiMe3 )2 ]2 , but isolated yields CuCl and [t BuAlO3 PC6 H4 CN]4 react to give crystals of
are very low. [Al(t BuAl)6 (O3 PC6 H4 CN)8 Cu(NCCH3 )2 ]x . This is a one-
Equimolar reactions of an aluminum alkyl with a dimensional polymer in which [Al(t BuAl)6 (O3 PC6 H4 CN)8 ]
phosphonic acid under room temperature or reflux conditions units are linked to Cu(NCCH3 )2 + moieties via two
yields oligomers of the formula [RAlO3 PR ]n (n = 4, 6, 10) of the cyanophenyl substituents. The core structure of
(equation 28).91,92 Tetrameric (n = 4) derivatives (37) are the [Al(t BuAl)6 (O3 PC6 H4 CN)8 ] can be described as two
Al4 P4 O12 cubanoids sharing a common vertex occu-
pied by an octahedral aluminum. The formation of this
nR3 Al + nR P(O)(OH)2 [RAlO3 PR ]n (28)
2nRH compound is not understood. Structural rearrangements
(n = 4, 6, 10) have been better-studied for analogous alkylgallophospho-
nates.
most common and are obtained in high yield. Three Fluoride is often used as a mineralizer and structure-
hexamers have been isolated and structurally characterized directing agent in the formation of aluminophosphate molecu-
as has the decamer [t BuAlO3 PMe]10 ,96 but these were minor lar sieves, some of which retain fluoride by encapsulation
components of mixtures that consist mainly of tetramers. in Al4 P4 O12 D4R cages.98 Attempts to encapsulate fluo-
The tetramers (37) possess a cubanoidal Al4 P4 O12 core ride in molecular compounds such as (37) have not been
structurally analogous to double-four-ring (D4R) SBUs highly successful. However, Roesky and coworkers were able
found in aluminophosphate molecular sieves. The drum-like to prepare the unique fluoride-containing aluminophospho-
Al6 P6 O18 core of hexameric derivatives resembles double- nate [Cs3 (THF)3 F(i BuAl)3 (t BuPO3 )4 ]2 [(i BuAl)2 (-F)2 (t BuP
six-ring (D6R) SBUs common to AlPO4 -18, AlPO4 -52, O3 )4 ].99 The encapsulated fluoride resides in an Al4 P4 O12 (-
and MAPOs isotypic to the aluminosilicates chabazite and F)2 F2 cage in which two aluminum centers each have an i Bu
faujasite. The structure of the decamer can be described as substituent and the remaining two aluminum centers have lost
two edge-opened tetramers linked via AlOP bridges to an their alkyl substituent and have fluoride bridges to two par-
eight-membered Al2 P2 O4 heterocycle. tial tetramers. Roesky and coworkers have also characterized
several aluminophosphonate cage compounds that incorpo-
rate alkali metal cations and these are described in a recent
R R review.92
Al O P Aluminum alkyls react with bulky silane triols to give
R O O
cage aluminosiloxanes that are structurally related to the
O R O molecular alkylaluminophosphonates.100 If these reactions are
P O Al
R
conducted in a 1:1 molar ratio cyclic dimers or cubanoidal
P O
O O Al aluminosiloxanes are obtained depending on temperature.
O R The cyclic dimer [i Bu(THF)AlO2 Si(OH)R]2 (R = (2,6-
O
i
Al
O
P Pr2 C6 H3 )N(SiMe3 )) is obtained at low temperature. It
R R contains an eight-membered Al2 Si2 O4 ring similar to that
found in the mineral gismondine. If the reaction of RSi(OH)3
(37) with Me3 Al or i Bu2 AlH is conducted in a 1:1 ratio at 65 C,
compounds [RSiO3 AlL]4 (R = N(Ar)SiMe3 , Co3 (CO)9 C;
L = THF, 1,4-dioxane) (38) are obtained. These contain
The tetrameric alkylaluminophosphonates (37) are ther-
an inorganic Al4 Si4 O12 core that is isoelectronic to the
mally quite stable and those with smaller substituents
sublime without decomposition. The most volatile of Al4 P4 O12 core of the aluminophosphonates (37) and analogous
these, [MeAlO3 PMe]4 , sublimes to give crystals at to the D4R SBUs common to some aluminosilicates (see
150 C/0.1 mm Hg. The tetrameric alkylaluminophosphonates Zeolites). Three oxygen bridges in the Al4 Si4 O12 cage
are also moderately stable to air and moisture. In contrast, and a neutral donor define the coordination sphere of the
the alkylaluminophosphate [t BuAlO3 P(OSiMe3 )]4 , which is approximately tetrahedral aluminum atoms. Organometallic
obtained from Me3 SiCl elimination upon reaction of t BuAlCl2 derivatives are obtained upon reaction of the silane triol with
with (Me3 SiO)3 P=O, is readily hydrolyzed. NaAlEt2 H2 or LiAlH4 to yield [Li(THF)]4 [RSiO3 AlH]4 or
Cage fragmentation and rearrangements have been [Na(THF)]4 [RSiO3 AlEt]4 , respectively. An aluminosiloxane
observed for some tetrameric alkylaluminophosphonates.97 with a drum-like Al4 Si2 O6 core is obtained if the
Reaction of [t BuAlO3 PMe]4 with acetylacetone in toluene at reaction of RSi(OH)3 to i Bu2 AlH is conducted with a
70 C results in precipitation of the decamer [t BuAlO3 PMe]10 . 1:2 ratio.
ALUMINUM: ORGANOMETALLIC CHEMISTRY 17
+
+
Et 2 O R OEt2
R3Al + B(C6F5)3 Al [RB(C6F5)3] (31)
O R OEt2
[Me2AlCl]2 O Me
+ Me Al O [Me2AlCl2] (29)
15-crown-5 and ether to form the structurally characterized salt
O
O [Me2 Al(OEt2 )2 ]+ [MeB(C12 F9 )3 ] .36
Jordan and coworkers have prepared cationic aluminum
complexes utilizing amidinate ligands using the alkide
abstraction route.103 Reaction of {MeC(Ni Pr)2 }AlMe2 with
The Me2 Al+ fragment is nearly linear with a CAlC B(C6 F5 )3 or [Ph3 C]+ [B(C6 F5 )4 ] yields the unstable cation
angle of 178 and an AlC distance of 2.00(2) A. [{MeC(Ni Pr)2 }AlMe]+ . The cation can be stabilized by coor-
Similarly, the reaction of [t Bu2 AlCl]2 with N ,N ,N ,N - dination of a Lewis base to give [{MeC(Ni Pr)2 }Al(Me)L]+
tetramethylethylenediamine (tmeda) gives [t Bu2 Al(tmeda)]+ (L = NMe2 Ph, Me3 P) or with one equivalent of the start-
[t Bu2 AlCl2 ] . Additional tmeda may displace the remaining ing amidinate complex to give the methyl-bridged com-
halide to give the base-stabilized cation with halide counterion, plex [{MeC(Ni Pr)2 }Al(Me)(-Me)Al(Me){(i PrN)2 CMe}]+ .
[t Bu2 Al(tmeda)]+ [Cl] . This is referred to as halide Jordan has structurally characterized a related three-coordinate
displacement or symmetric cleavage. Cationic complexes can aluminum cation supported by a -diketiminate ligand (39)
also result from ligand redistribution as in the formation of and a methyl-bridged dimer (40) supported by an aminotropon-
the first aluminocenium cation [Cp2 Al]+ [Cp AlCl3 ] from iminate ligand.104,105 The aluminum atom in (39) is perturbed
18 ALUMINUM: ORGANOMETALLIC CHEMISTRY
N
(41)
Al Me [B(C6F5)4]
N
Ar Polyhedral borane and carborane anions are more robust
and less coordinating than the perfluoroarylborates and thus
Ar = 2,6-iPr2C6H3 may serve to stabilize reactive alumenium species. Reed
(39) and coworkers reacted [Ph3 C]+ [CB11 H6 Br6 ] with Et3 Al
to give [Et2 Al][CB11 H6 Br6 ].109 The molecular structure
of [Et2 Al][CB11 H6 Br6 ] shows an approximately tetrahedral
iPr + aluminum coordinated by two of the bromine atoms of the
carborane anion with distances of 2.581(2) and 2.542(2) A.
N
iPr Me The compound is formulated as a tight-ion pair, [Et2 Al]+
Al
[B(C6F5)4] [CB11 H6 Br6 ] , and shows alumenium ion-like behavior. It
N Me N
Al i
reacts with pyridine to form [Et2 Al(py)2 ]+ [CB11 H6 Br6 ] ,
Pr likely coordinates ethylene, and effects alkylation of benzene
N Me
i
and formation of butene.
Pr
(40)
Mes +
Mes
polyether elastomers find use in automotive and industrial suffocation. Slow oxidation will continue to take place until
applications that require materials with low gas permeability, the material is consumed. The absorbent should be disturbed
retention of flexibility at both low and high temperatures, periodically to expose fresh material to air. When all material
and stability upon extended exposure to heat, hydrocarbons, appears to be oxidized, a mist of water can be used to hydrolyze
and ozone. Catalysts are the so-called Vandenberg catalysts any remaining organoaluminum compound. Solid waste can
prepared by partial hydrolysis of aluminum trialkyls, often then be collected and disposed of in a suitable hazardous
with additional components such as acetylacetone. Annual waste container.
production of polyether elastomers using aluminoxane- Sand and vermiculite can also be used to suffocate a fire if
based Vandenberg catalysts was estimated at nearly 13 the spill ignites. In the case of a fire, standard dry chemical
000 tons in 1991. Several research groups are developing (BC, sodium bicarbonate) extinguishers are used to suffocate
organoaluminum catalysts for polymerization of epoxides, the fire and suppress the burning process. Carbon dioxide
lactones, and lactides, as well as for copolymerization of extinguishers can also be used to suffocate and cool the fire.
carbon dioxide and epoxides.118122 These efforts have not yet Obviously, water cannot be used.
resulted in commercial processes. Severe burns can occur if exposed skin comes into contact
Organoaluminum compounds are also utilized as precur- with an aluminum alkyl, either neat or in solution. The
sors for the preparation of aluminum-containing materials. severity and depth of the burn will increase with increasing
Electronic-grade trimethylaluminum is sold in 99.9999% exposure time. In case of an accident, rinse the exposed skin
purity for the production of semiconductors (see Semicon- with copious amounts of water to hydrolyze any remaining
ductors) and other electronic-grade metal alkyls. Aluminum aluminum alkyl, to dilute the reagent, and to cool the skin.
trialkyls and a variety of organoaluminum alkoxides, halides, Rubber gloves, goggles, and a lab jacket are required when
amides, azides, and -diketonate derivatives continue to be working with aluminum alkyls. A splash-protective face shield
studied as single-source precursors to thin films of Al2 O3 , and a separate safety shield are also recommended.
AlN, AlGaAs, and AlGaSb by MOCVD, MOVPE and other Small quantities of organoaluminum distillation residues
pyrolysis methods.123126 High-purity films of aluminum can and waste solutions may be destroyed by slow addition of a
be deposited by thermal decomposition of aluminum alkyls, 25% isopropanol solution in a hydrocarbon solvent. Safety
particularly those that possess a -hydrogen. procedures for handling large volumes of organoaluminum
reagents can be obtained from commercial vendors.
9 SAFETY CONSIDERATIONS
10 RELATED ARTICLES
The safe handling of organoaluminum compounds, partic-
ularly aluminum trialkyls, requires procedures to minimize Alkali Metals: Organometallic Chemistry; Aluminum:
the risk of exposure of the organoaluminum reagent to Inorganic Chemistry; Beryllium & Magnesium: Organometal-
oxygen, water, halogenated solvents, excessive heat, and lic Chemistry; Boron Hydrides; Boron: Organoboranes;
ignition sources.7 Exposure to oxygen and water is min- Boron: Polyhedral Carboranes; Gallium: Inorganic Chem-
imized by handling organoaluminum compounds in dried istry; Gallium: Organometallic Chemistry; Indium: Inorganic
glassware under an atmosphere of purified nitrogen or argon. Chemistry; Indium: Organometallic Chemistry.
This is accomplished using standard inert-atmosphere tech-
niques on a dual-manifold Schlenk or vacuum line, or in an
inert-atmosphere glove box. Liquid transfers between septum-
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Ammonia & N-donor M N
M N H M
H
N H M
H
N H
M N N M N N H M N N M N N H
1 Introduction 1 H H
2 Ligands Containing Only One N-atom 4 Dinitrogen Diazenido Diazene Isodiazene
3 Ligands Containing Two N Atoms 8 (5) (6) (7) (8)
4 Catenated N Atoms 13
5 Polyamine Ligands 16
6 Miscellaneous Nitrogen Donor Ligands 21 H
7 Reactions of Coordinated Nitrogen Ligands 22 M N N H M N N H M N N H
8 Supramolecular Assemblies 23
9 Conclusion 24 H H H H H
10 Related Articles 24 Hydrazido(2-)-N,N
11 Further Reading 24 (9) (10) (11)
12 References 24
H H
H
M N N N H M N C N H M N N C
Glossary H
H
Triazene Aminidinate
Amine complex: complex with amine ligands, other than
(12) (13) (14)
ammonia
Ammine complex: complex with NH3 (ammonia) as the only
N-donor ligand, for example, trans-PtCl2 (NH3 )2
Nitrogen forms catenated2,3 (see Catenation) ligands such
Facultative ligand: multidentate ligands that are capable of
as N3 , as well as mixed donor atom ligands such as NCS ,
arranging their donor atoms around a metal ion in a number
NCO , CN , NO, NS, NO2 , NH2 OH46 (see Mixed Donor
of different ways
Ligands). We will restrict the present discussion to those
Homoleptic Complex: complex with only one type of ligand
ligands containing only N, C and, H atoms.
The equilibrium
Abbreviations R3 N + H3 O+
R3 NH+ + H2 O (1)
Table 1 Representative protonation constants for some N-donor Isomer, Types of ) or react (via MN bond rupture) with
ligands7 half-lives (see Radioactive Decay) of longer than 1 min. The
latter involves the hard-acid, soft-base concept12 with the
pK1
amine nitrogen being considered as a hard center (see Hard
L pKn [H+ ] pK1 [Ni(L)]10 [Cu(L)]10
& Soft Acids and Bases), as it binds strongly to protons,
en 7.18, 9.98 7.35 10.5 and is thus expected to bind strongly to hard metal centers
dien(159) 4.47, 9.17, 9.96 10.7 15.9 (good lone pair acceptors). In this classification, it is usual
trien(178) 3.6, 6.84, 9.22, 9.92 14.4 20.1
to compare the accessibility or stability of MN complexes
tetren(207) 17.4 22.8
penten(223) 19.1 with those of analogous MP donor ligands (a typical soft
donor). In both methods of classification, the boundaries are
not sharp and the stability of a particular metal amine com-
plex depends to a considerable extent on the nature of the
reaction of a coordinated water molecule by the incoming
ligand. For example, most open chain Cu2+ amine complexes
N-ligand, and there may also be competing hydrolytic
such as Cu(tetren)2+ (15) (207) are rapidly decomposed in
equilibria (equation 3). Such hydroxo
acid solution, but when the Cu2+ is encapsulated in an N5
polyamine cage such as L (16), the resulting complex is
MOH2 n+
M(OH)(n1)+ + H+ (3)
stable for days in 1 M HClO4 at 50 C13 (see Macrocyclic
Ligands).
complexes can be much more substitution-inert, and may also
result in metal ion hydroxide precipitation. The competition
can be overcome to a certain extent by using nonaqueous H
solvents, for example, DMSO or DMF in CrIII N-ligand NH N
Me
synthesis.8,9 NH NH N N
For labile systems with reasonably well defined coordina- Cu Cu
tion numbers, for example, first-row transition metal divalent NH2 NH2 N N
cations, chelating and macrocyclic ligands have a greater sta- Me
bility than would be expected from an additive relationship, [Cu(tetren)]2+ [CuL]2+
that is, from equations (4) and (5), KML > KML2 . However, (15) (16)
there is a simple relationship
Table 2 Structural effects on base hydrolysis rates (equation 7)1416 and (22), (23).20 It should be noted that current nomenclature
systems1 are not sufficient to distinguish between isomers (22)
Complex kOH (25.0 C)(M1 s1 ) and (23) (see, however, Reference 21).
CoCl(en)2 (MeNH2 )2+ 7.3
CoCl(en)2 (py)2+ 332
cis--CoCl(trien)(NH3 )2+ (193) 10.6 Cl + Cl +
H
cis-2 -CoCl(trien)(NH3 )2+ (195) 4.8 104
-CoCl(bispicdien)2+ (see 218) 2.0 107 N NH2 N NH2
t-CoCl(dmptacn)2+ (18) 4 102 Co H Co
t-CoCl(dmpmetacn)2+ (19) 7 101 NH3 NH3
NH2 NH2
Cl Cl
R(20) S(21)
An essential requirement in the SN1 CB mechanism for
Optical isomers of trans-[CoCl2(2,3-tri)NH3]+
reaction (7) is the presence of an NH proton. There are now
several polyamine ligands that have either one (18) or zero
(19) such protons (see also Section 5.3). Despite having zero
Cl 2+ Cl 2+
NH protons, [CoCl(dmpmetacn)]2+ reacts with base at a H
rate proportional to the OH concentration and faster than N N N NH2
[CoCl(dmptacn)]2+ (Table 2). Proton exchange at the CH2 Co H Co
position in the pyridyl arm trans to the leaving group was NH2 NH2 NH2 NH2
NH2 NH2
observed, and amido activation through the pyridine ring
is believed to be responsible for the OH dependent rate (22) (23)
law.16
Structural isomers of mer-[CoCl(3,3-tri)(en)]2+
R
The interchange of the stereochemically significant
N sec-NH proton in (20) (21) (inversion) or (22) (23)
(isomerization) is a base-catalyzed process and takes place via
N N a deprotonation protonation mechanism. This interchange is
one of the simplest types of reaction of a coordinated ligand,
and proton exchange rates have been measured for quite a
N N number of inert transition metal amine complexes.22 With
suitable central metals (PtIV )23 or ligands,24 the deprotonated
intermediates can be isolated and characterized. Other
(18) Dmptacn (R=H) reactions of coordinated amine ligands will be considered
(19) Dmpmetacn (R=Me) in Section 7.
Amines containing a Chiral carbon center in the aliphatic
residue attached to the nitrogen atom, for example, -methyl
For aliphatic amines, coordination of the lone pair to a benzylamine (24), (25), are of considerable interest to the
central metal ion completes the tetrahedral stereochemistry coordination chemist as, when coordinated, these ligands
about the nitrogen atom (equation 8), and induce chirality in the metal ligand chromophore. Methods
for the resolution of more than 1000 racemic nitrogen
n+
containing organic compounds have been described.25
R1 R1
(8)
Mn+ + N R2 M N R2
H NH2
R3 R3
NH2 Me H Me
C C
nitrogen bases with three different substituents now become
potentially chiral. Inversion about the nitrogen center is
generally rapid for labile complexes, but for inert complexes,
both geometric and optical isomers can be isolated.14,17,18
Although such isomers have not been resolved for
monodentate amines (suitable tertiary amines19 are not easily
coordinated to inert metal centers), the phenomenon is quite (R)(+)aMethylbenzylamine S()aMethylbenzylamine
widespread with coordinated aliphatic polyamines (20), (21) (24) (25)
4 AMMONIA & N-DONOR LIGANDS
cially available, but designer specific ligands26,27 require the N N M N
use of conventional organic synthetic techniques.28,29 Methods M M CH2
M
of amine complex synthesis are usually central-metal specific,
(29) (30) (31)
but summaries of procedures used for CrIII8,9 and CoIII30 are
available. In the case of the inert metal centers, geometrical
isomers are frequently encountered. Fractional crystallization R M R
is still widely used for isomer separation procedures,14 but M N C N C M N M
column chromatography has the potential for separation of R M R
both optical and geometric isomers and the advantage that (32) (33) (34)
isomers or by-products at the 1% level can be detected and
concentrated (see Section 5.2).3134
Molecular Mechanics calculations can be used (1) in the Complete deprotonation gives the exceptionally strong
analysis of disordered structures, (2) in the prediction of -donor N3 anion (see -Bond). Complexes such as
known structures, (3) in the prediction of isomer ratios, OsVII Br4 N or [OsVIII O3 N] have OsN bonds in the
and (4) in the prediction of conformer ratios. The majority 1.6 1.8 A range, and the N3 ligand has a strong Trans
of studies have dealt with CoIII hexaamine systems,35 but Influence. The available Lone Pair (1), allows such complexes
now36,37 force fields are available for amine complexes of to act as ligands forming bridged nitrido species (34).
CoII , NiII ,38 CuII , ZnII , CrIII , FeIII , and RhIII . Rearrangement of the bonds leads to triangular planar N-
centered systems (29), such as [IrIII
3 N(SO4 )6 (H2 O)3 ]
6
and
tetrahedral M4 N (30) arrangements, such as [(Ph3 PAuI )4 N]+
+
PPh2Me PPh2Me
trans-CrCl2 (2, 3, 2-tet)+ + NH3 (l)
adopt linear (32) and bridged modes (33).41 In (33), there is a trans-CrCl(NH3 )(2, 3, 2-tet)2+ + trans-Cr(NH3 )2 (2, 3, 2-tet)3+
striking analogy with alkenes.
(10)
H H H
somewhat analogous to water.45
N N M N
H NH3 (g) is extremely soluble and the aqueous solution is
M M M M
best described as NH3 (aq) with the equilibrium (pKb 25 =
(26) (27) (28) 4.75) written as equation (11). Thus, NH3 (aq) (1 M) is an
AMMONIA & N-DONOR LIGANDS 5
important laboratory source of NH3 , NH4 + , or OH . Table 4 Acid hydrolysis rates (kH )
for some [M(CF3 SO3 )(NH3 )5 ]n+
complexes at 25 C
NH3 (aq) + H2 O
NH4 + + OH (11)
M kH (s1 )
Almost all cations show some sort of interaction with the
CrIII 0.125
NH3 molecule.46 For M(NR3 )x n+ systems, the maximum x is RuIII 0.093
often achieved with ammonia. CoIII 0.027
The ammine chemistry of group 2,47 group 3,48 CoIII ,30,42 RhIII 0.019
III 8,9,49
Cr , RuIII/II ,4751 and OsII ,49 has been reviewed. OsIII 0.0018
Synthetic procedures for many ammine complexes are given IrIII 0.00026
by Schlessinger.52 Table 3 lists some (sometimes exotic) PtIV <0.0001
salts of representative ammine complexes, together with the
average metal NH3 bond distance and an estimate53 of the
average M NH3 bond energy. X N
Transition metal ammine cations have been used in the N N N X
isolation of unusual anions. M M
N N N X
CoIII and CrIII ammines were among the first to be X N
investigated by Reinecke, Jrgensen, Werner (Nobel prize, trans-(36) cis-(37)
1912), and Pfeiffer in the early days of coordination chemistry
(see Coordination Chemistry: History), and this work
continues today (Taube, Nobel Prize, 1984). [MX(NH3 )5 ]n+
and the isolation of the other isomer is still a challenge to the
(X = anionic or neutral group) is particularly well-studied14
synthetic chemist.
and has even been used as a protecting group in peptide
For the triammines, there are two potential isomers
synthesis. Variation of M has a considerable influence on the
[mer-(38) and fac-(39)] (these are now to be called OC-6-
rate of the Solvolysis of X (Table 4).
12 and OC-6-22 respectively, although the ranking order
Two possible isomers [trans-(36), cis-(37)] for [MX2
may change with X1 ). [Co(NO2 )3 (NH3 )3 ]52 should be a
(NH3 )4 ]n+ (M = inert transition metal) are usually separable,
nonelectrolyte using Werners octahedral coordination ideas,
although in a number of cases only one isomeric form is known
but should be an electrolyte according to Jrgensens chain
theory. Both schools succeeded in preparing compounds
with the above stoichiometry with the Werner sample being
Table 3 Typical ammine complexes52 a conductor and the Jrgensen sample a nonelectrolyte!
The situation was finally resolved when it was shown
MNH3 (av.)53
MNH3 (av.) bond energy that the Werner sample was heavily contaminated with
Complex distance (A) (kJ mol1 ) [Co(NO2 )2 (NH3 )4 + ][Co(NO2 )4 (NH3 )2 ]52 and hence was
conducting. Even today, it is sometimes difficult to establish
[MgII (NH3 )6 ](ClO4 )2 176.8
the configuration of, say, [Co(N3 )3 (py)3 ], without resource to
(NH4 )2 [VIII Cl5 (NH3 )] 2.138
[CrIII (NH3 )6 ]ZnCl4 Cl 2.071(3) X-ray crystallography.
FeIII N 2.00(est)
FeII N 2.15(est)
[RuII (NH3 )6 ]I2 2.144(4) N N
[RuIII (NH3 )6 ](BF4 )3 2.104(4) X X N N
[CoII (NH3 )6 ]Cl2 2.114(9) 186.4 M M
[CoIII (NH3 )6 ](Hg3 Cl9 ) 1.971(7) 389.3 X N X X
N X
[NiII (NH3 )6 ]2+ 2.15 197.3
c-[PtII Cl2 (NH3 )2 (HgCl2 )3 ]n 2.093(17) mer-(38) fac-(39)
[PtII (NH3 )4 ][PtIV Br2 (NH3 )4 ]
(HSO4 )4 2.059
[CuI (NH3 )2 ][Ag(NCS)3 ] 2.00 128.0
[CuII (NH3 )6 ]Cl2 2.07(7) eq 213.5
Despite intensive work, few metals give a complete
2.62(11)ax monotonic series [MX6x (NH3 )x ](x3)+ , x = 0, 1 . . . 6 (X =
K[CuII (NH3 )5 ](PF6 )3 2.00, 2.048 eq Monodentate Ligand). The missing member is usually the
2.193ax x = 1 compound, with the most extensive examples being
[CuII (NH3 )4 ]I4 2.025(8) M = CrIII , X = NCS (x = 1) or H2 O8 ; M = CoIII , X =
[AgI (NH3 )2 ][AgI (NO3 )3 ] 2.114 106.6
NO2 (x = 1).
[ZnII (NH3 )6 ](I3 )2 2.05(1) 218.9
[CdII (NH3 )6 ]I4 2.341(8) 191.7 Some ammine complexes are metal ion specific, for
example, the dinuclear CoIII -peroxo and -superoxo (see
6 AMMONIA & N-DONOR LIGANDS
6+
(NH3)5Co O n+ 4+ (NH3)5RuIII O RuIV(NH3)4 O RuIII(NH3)5
O Co(NH3)5 (NH3)5Cr O Cr(NH3)5
(48)
(40) (41)
n = 4, brown peroxo bridged
2+
n = 5, green superoxo bridged Cl
(NH3)3RuII Cl RuIII(NH3)3
n+ Cl
(NH3)5Ru N N Ru(NH3)5
(49)
(42)
n = 4, 5, 6 6+
H3N NH3 H2O OH2 H3N NH3
6+
H2O Os N Os N Os OH2
Co(NH3)4
OH H3N NH3 H2O OH2 H3N NH3
OH OH
Co (50)
(NH3)4Co
OH OH
OH
3+
Co(NH3)4 H3N NH3 H3N NH3
50 82
NH2 NH2
83 161
CH2NH2 CH2NH2
106 134
NH2 NH2
H 177 H 187
C NH2e C NH2f
CH3 CH3
a
Available as the anhydrous liquid or as a 28% aqueous solution ( = 0.880). b Available as the anhydrous liquid,
or as a 40% aqueous solution ( = 0.902). c Available as the anhydrous liquid or as a 70% aqueous solution
( = 0.796). d (S) (+): D = +7.8 . e (S) (+): D = +3.8 . f (R) (+): D = +30 .
C C 4+
(NH3)5Ru N N Ru(NH3)5
N N N N
C C Pt C C C C Pt C C (59)
N N N N
C C C C C C
(53) (54) N
M N N M N N M M
N
systems (equation 7). For pyridine (57), complexes64 such as (60) (61) (62)
t-[RhCl2 (py)4 ]+ probably represent the maximum number
of py ligands that can bind to an inert central metal.
Similar stereochemical restrictions probably apply to the
Complete protonation of dinitrogen results in hydrazine,76
four-coordinate CuII complexes of N-Me-imidazole65 (see
which can bind through either one (11) or both (bridging) N
78) and 1,2,4-triazoles,66 but six-coordinate [MII (LH)6 ]2+
atoms, but high oxidation state metals are readily reduced.77
(LH = pyrazole, 77) are known for all first-row divalent
The nomenclature for substituted hydrazines is very
transition metal ions.67 While the N-bonded chemistry of
confusing (63 67).78 Three types of ligands are available
pyrrole (58)68 is only poorly developed, that of piperidine (55)
with a formal double bond between the two N atoms (1)
is quite well established.69
diazenido (6), obtained from diazonium compounds (ArN2 + ),
(2) 1,2-diazines (7) (azo compounds, ArN=NAr), and
(3) 1,1-diazines (8).
NH
NH N
H H H H 1 H H 2
NH2
H N N H N N H N N
(55) Piperidine (56) Aniline (57) Pyridine (58) Pyrrole
(63) Hydrazine (64) Hydrazido(-l) (65) Hydrazido(2-)-N,N)
(diazanido) (diazane-1,2-diido)
N N H
N N H
The dinitrogen complex [RuII (N2 )(NH3 )5 ]2+ (60), (66) Hydrazido(2-)-N,N (67) Hydrazido(3-)
described in 1965 by Allen and Senoff, led to much subsequent (diazane-1,1-diido) (diazanetriido)
research related to nitrogen fixation.7075 The reduction of
coordinated N2 in simple systems is shown in Figure 1, but the
hydrazido(-2) (9) system is the only coordinated intermediate
characterized in the conversion of N2 to NH3 . The coordinated The diazenido ligand can be regarded as RN2 + , RN2 , or
dinitrogen (60) may also act as a bridging ligand (59), (61), RN2 and when coordinated, there is a considerable range in the
and (62) N2 forms reasonably stable and well characterized observed N=N stretch (2100 1440 cm1 ). Obviously, there is
complexes74,75 with RuI/II , OsII , Mo0 , W0 , Mn0 , Co0/I , Ta0 , a close analogy between NO and RN2 as ligands.4,78 Diazines
Ti0 , Ni0 , Zr0 , and IrI . can be formed from diazenido complexes by electrophilic
H+ H+ 2H+
M N N M N N H M N NH2
M(H) NH NH2
NH3
N2 H+ N2H4
NH3
2H+ 2H+
M N
M NH3 M N H
M N M N
H+
repetitious exposure. It can adopt either the cis (gauche) (69)
N R N R
(13) or trans (70) conformations with an energy difference of about
NH2 N N
C C
(68) N M N N M N
C C
3.1.1 1,2-Diaminoethane and related ligands (73) d (74) l
example, (75 77), it is not possible to separate the , used. Here, the two possible chelate ring conformations
conformational isomers as these exist in equal amounts in are named lel or ob when the central CC bond of
the solid state (see also the discussion with respect to structure the diamine ring is (approximately) parallel or oblique
(220)). Introduction of a second chelating ethylenediamine with respect to the C3 symmetry axis of the [M(en)3 ]n+
into the coordination sphere gives rise to two geometric complex.35,87 The four conformers are symbolized as lel3 ,
isomers, trans-(78) and cis-(79), (see also (36) and (37)). lel2 ob, lelob2 , and ob3 , with lel3 being equivalent to ()
The diamine rings in (78) and (79) can be either ,; , or, or (). In the solid state, the actual ring conformations
,; in (78), the , and , conformations are enantiomeric adopted in [M(en)3 ]n+ complexes depend on the anion
and energetically equivalent, and are estimated to be about and are apparently related to the degree of hydrogen
4 kJ mol1 more stable than the trans , form. In the solid bonding.35,42
state, however, the majority of the square-planar [M(en)2 ]2+
(M = Ni, Cu) and trans-[CoX2 (en)2 ]+ complexes adopt the
, conformation.42 cis-Bis(bidentate chelate) complexes like
(79) lack a plane of symmetry and thus have the potential
to be separated into enantiomeric (80), (81) forms. M M
The separation of -cis-[CoBr(en)2 (NH3 )]2+ into the
and forms88 using the method of racemic modification
(Werner, 1911) was perhaps one of the most significant (82) -M(en)3n+ (83) -M(en)3n+
achievements in the development of modern coordination
chemistry. Approximately 10% of racemic systems like (80),
(81) form conglomerates89 on crystallization (spontaneous
resolution), and such systems are under active investigation.90
NH2 NHMe NH2 NH2
0 Cl +
NH3 3+ (84) (R or S at when coordinated) (85) (R or S at )
NH2 Cl NH2 OH2 NH2 NH3
Pt Cr Co
NH2 Cl NH2 OH2 NH2 NH3 Many N and C-substituted ethylenediamine ligands are
Cl NH3 available.35,42 A single substituent on the N-atom will give
(75) (76) (77) an unsymmetrical prochiral ligand (84), and on the C
atom the unsymmetrical ligand is racemic (85). Symmetrical
substitution on both C atoms will give meso (86) and racemic
X ligands (87).
X
M M
X
X
NH2 NH2 NH2 NH2
(78) trans (79) cis
(86) meso (R, S at ) (87) racemic (R,R or S,S at )
H (S) Me H (S) Me
Me C C Me
H H N N
(88) (89) Cu
N3 N3
fully C-alkylated isomer 2,2,3,3-Me4 en35 in the coordination
(90)
chemistry literature.
If the two amine groups are located in the 1,2- (or
1,3-)92 positions of a cycloaliphatic ring, there is potential rings can be incorporated into the skeleton of polyamine
for both geometric and optical isomers. The most widely ligands.
studied of such ligands is cyclohexane-1,2-diamine (chxn).35
The commercially available free base is available as a (not
always equal) mixture of the cis-(R,S)- and trans-(RR,SS)- 3.1.3 Heterocyclic Ligands with Two N Atoms.96103
isomers, conveniently separated via the NiII complexes with
yellow, diamagnetic [Ni(cis-R,S-chxn)2 ]Cl2 being insoluble This section covers the vast field of the coordination
in MeOH. After pH adjustment, and addition of water, chemistry of pyrazole (91), imidazole (92), pyrazine (93),
the mother liquor deposits crystals of blue, paramagnetic pyrimidine (94), pyridazine (95), 2,2 -bipyridine (96), o-
trans-[Ni(trans-(RR,SS)-chxn)2 (H2 O)2 ]Cl2 . The amines can phenanthroline (97), piperazine (98), and dabco (99) as
be recovered (as hydrochloride salts) from the NiII complexes ligands.
by decomposition with HCl, and the trans-(RR,SS)-chxn can
be resolved into the ()589 -(R,R) enantiomer with (+)589 -
(R,R)-tartaric acid.93,94 NH
N N N N
N
H
3.1.2 1,3-Diaminopropane and Related ,-Aliphatic (91) Pyrazole (92) Imidazole (93) Pyrazine
Diamine Ligands
L N N L
HN N N
Ni Ni N N N N
L N N L
L L (106) (107)
(102) HN
N N
HN N N
N N
In the six-membered diazine systems, (93 95), the most (108) (109)
widely investigated ligand is pyrazine (93)96,97 in the model
pyrazine bridged mixed valence compound (103) (see Mixed
Valence Compounds and Creutz Taube Complex). The NH HN N N
coordination chemistry of the aliphatic analog, piperazine
(98), is not well developed. N N N N
The chelating ligands, 2,2 -bipyridine (bipyridyl) (96)98100 (111)
(110)
and o-phenanthroline (97), have distinctive metal com-
plexes. When compared to say 1,2-diaminoethane, bipy
is less basic, more rigid, and larger; when coordinated, N N
the ligand orbitals can participate in an extensive - N N
overlap with the metal orbitals. Consequently, not only N N N N
do bipy and related ligands bind to metals that form (112) (113)
strong complexes with en, but these ligand systems also
form complexes with metal centers such as FeII /FeIII that
have only a poorly developed aliphatic polyamine chem- The combinations are limited only by imagination and the
istry. coordination chemistry of many of these systems is yet to
AMMONIA & N-DONOR LIGANDS 13
NH2
N N N N
(114) NH2 N N
(122) (123)
R N N N R
H
(117) (124) R = Ph
N
NH2 N N
HN N N
N NH2 N
N N
(118) (119)
Cr Cr
N N
N
N N
N
N NH2 N NH2
Cr Cr = 1.85
(120) (121) (127) Cr2(PhN3Ph)4
Also included here is 1,2-diaminobenzene (122) (o- The central N atom in the triazine system can be
phenylenediamine), kept separate because of its tendency replaced by the CH group to give imidines (13),41,105 and
for internal redox reactions (equation 19)42 and the bidentate complexes with structures similar to (125 127) are known,
14 AMMONIA & N-DONOR LIGANDS
N R
N N
N
Cu Cu M
N N
N N
N Cu N R
N N Cu Cu (135)
N
N Cu N N N N
N N Further catenation of the nitrogen chain leads to
pentazadienes (136) with bridging structures (137) and (138)
Cu....Cu = 2.451 Cu....Cu = 2.66
for the NiII and CuI complexes, respectively.
(128) R = Ph (129) R = Me
H
for example, [Mo2 (PhNC(Ph)NPh)4 ]. However, no complexes
containing fully saturated triazanes (130) or tetraazanes (131) R N N N N N R
appear to have been described. On the other hand, both (136) R = p-tol
tetrazines (132) and tetrazadienes (133) form stable metal
complexes,2,105 despite the fact that the parent tetrazadienes
do not exist in the free state. N N N N
N N N
N N N N N
N N N Cu Cu Cu
R2N N(R) NR2 N Ni Ni
N N N N N
(130) N
N N N N N N N N N N
N N N
(137) (138)
H2N NH NH NH2
[Ni2(136)4] [Cu3(136)3]
(131)
4.1 Azides
R2N N N NR2
(132) R = Et The azide ion (N3 ) is a Pseudohalide105,106 because
its properties resemble those of the halides. The free ion
has a linear N N N skeleton with equal N N distances
R N N N N R (1.167 A), but the anion coordinates terminally (137A) with
(133) an M N N angle of 116 140 and an N N N distortion of
about 4 from linearity. Other possible modes of coordination
are shown in (137B) (144). As yet, there are no examples
The N atoms in (133) can be replaced by C atoms to give of (143).
1,4-diaza-1,3-butadiene systems (134)105 that have a close
skeletal relationship to bipyridyl ligands (96) (Section 3.1.3).
N N N M
N N N
M M
1.457
(137A) (137B)
R N
120.8
N N N M
N R N N N
M N N N
1.258 M M
(134) R = Cyclohexyl (139) (140) m-(1,1)
The bond lengths and bond angles in (134) suggest little The azido ligand is particularly versatile as a leaving
electron delocalization in the free ligand, and rotation about group, as the displacement is acid catalyzed.107 Coordinated
the C C bond allows coordination in the planar chelating azide ligands also have the potential to react via 1,3-dipolar
mode (135). cycloaddition with organic isonitriles or nitriles to give 1- or
AMMONIA & N-DONOR LIGANDS 15
M (3)
N N N N
M N N (2)
M M N N N
N N (1)
N N N M N H
(141) m-(1,3) (142) m-(1,1,1) (145) Triazine (146) Triazole
M M M M
N N N N N N NH2
M M M H
N N
(143) m-(1,1,3,3) (144) m-(1,1,3) N N
N N
N
N
5-substituted tetrazolate anions (Section 4.2) respectively H
(equations 16 and 17). Alternatively, the azide ion can be (147) Benztriazole (148) 8-Azaadenine
added to coordinated
R N N
M N N
N M N
M N3 + RNC M
N
(16)
N
N N
(149) (150)
M N
M N3 + RCN N N (17) N N
N
N N N N
R
M H M M
(2) (3) H R
(1) N N N N N
H N N (4) N N
(5) N
N N N N
H H
(156) (157)
(168) (169)
N N
N
N
(158) 1,5-Pentamethylenetetrazole N
N N
R R
5 POLYAMINE LIGANDS (170)
N N H2N NH NH NH2
N N
N N
(184)
(175)
OBz NH2
+
OBz NH2 NH NH NH2
NH2
(185)
OBz NH2
OBz +
NH2 NH NH
OBz NH2
NH
(186)
NH NH NH2
BzO OBz
+
BzO OBz NH NH NH2
NH2 NH2
(187)
(188)
OBz NH2
+
OBz NH2 NH2 NH N NH2
OBz
(189)
NH2
N N NH2
N N
N N N
H2N
(190)
H2N NH2
(191) (192)
H N H N
N N N N N N
M H M H
Y X N X N N
N Y
cis-a or ff cis-b1 or s-fms
(193) (194) N N N N
N X
H H
N
(202) bistpa
N N N
M H M H
N Y N N
X Y Ar Ar
cis-b2 or p-fms (R,R)-transa or msma H H N N
(195) N N
(196)
N N
X Y N N N N
H H H H
N N N N
M M (203) (204)
N N N N
Y X
(R,S)-trans1 or msms (R,S)-trans2 or mama
(197) (198)
NH N
NH2 NH2
N N NH HN
N N N HN NH
M M
H2N X X NH2
NH N H
(210)
fff ffms
(216) (217)
N
NH2 NH2
N NH
N
N HN NH HN NH
N NH M
NH2 NH2 NH2 NH2 M
N NH2 X NH
X
N NH2
(211) (212) H
ffma fmf
(218) (219)
H
NH2 NH2
N H H H
NH2 NH2 NH2 NH2 NH2 N N N N
N N
M M
H
Me N N N N Me H2N NH H2N NH
X X
fmsms fmsma
(213) (214)
(220) (221)
NH2
N N N N N
N M
R N H H
H2N NH
X
(215) fmama
(222)
3+
the isolated [Co(bpytrien)] isomer(233) has the ffma f
configuration.137,138 Structures (225) and (226) are also Figure 4 Possible topological arrangements for a linear facultative
available with different C-atom chain lengths.42 The violet N5 polyamine in an octahedral complex14,21
NiII complex of (226) also has all six N atoms bound but there
are two crystallographically distinct cations in the unit cell,
differing in conformation of the central N(CH2 )2 N chelate
ring.139 The sexipyridine ligand (228) binds to MnII , FeII , NH2 NH NH NH NH NH2
CoII , NiII , CuII , ZnII , CdII , and HgII to form six-coordinate
[M2 (228)2 ]2+ in a symmetrical double helical arrangement128
(see Section 8) and ZnII , CdII , and HgII complexes are known (224)
for (232).140
Ligands (227) and (229 231) are major products from the
synthetic strategy shown in Figure 2.124
H2N NH2
N N
HN NH N N N
N
NH2 NH NH NH NH NH2
H2N NH2
(223) (225) (226)
AMMONIA & N-DONOR LIGANDS 21
H
H H2N N NH2 H2N N NH2
NH NH2 H2N N NH2
R HN NH HN NH
N N NH NH M M
NH NH2 n n
N 4
(234) (235) [M(big)n] (236) [M(bigH)n]Xn
NH NH2
H
HN N NH
(229)
NH NH2
NH2
NH NH2 NH NH NH2
NH2
NH NH2 NH
NH2 HN N NH
NH NH2 NH H
(230) (231) (237)
NH NH H2N N NH2
N NH NH
N
(233) Bpytrien Figure 5 Synthesis of [Cu{en(big)2 }]SO4
22 AMMONIA & N-DONOR LIGANDS
NH2
4H
N L5 MNH2 CH2 Me L5 MNCMe (20)
N N
NH2
N N N N can yield imines or nitriles (equations 18 20) if the M N
H H bond is sufficiently inert.
(240) (241)
7.1.2 Condensation13,147,148
2+ 2+
(242) (243)
H2N NH2 O H2N NH
Ni + Ni OH
H2N NH2 H2N NH2
H2N NH
A variety of reactions can take place with coordinated Ni
H2N NH
nitrogen ligands. In many instances, the products are
controlled by the template effect (see Templating). In other
cases, coordination can induce a dramatic increase in the
reaction rate. Figure 6 Carbonyl condensation
AMMONIA & N-DONOR LIGANDS 23
2+
Finally, reactions of coordinated ligands can produce
NH N amines. These include oxidation of coordinated thiocyanate
(equation 23) and hydrolysis of coordinated cyanate (equa-
Ni
tion 24).152
NH N
[O]
trans-[Co(NCS)Cl(en)2 ]2+ trans-[CoCl(NH3 )(en)2 ]2+ (23)
H+
[Cr(NCO)(NH3 )5 ]2+ [Cr(NH3 )6 ]3+ (24)
Oxidative deamination followed by carbonyl condensation melt
is thought to be the pathway by which mer-tridentate imine Cr(NO3 )6 9H2 O + urea
[Cr(NCO)(NH3 )5 ]2+ (25)
130 C
systems are isolated from diamine precursors (Figure 7) using
Co as the metal center.149
A number of reactions of inert metal complexes are While much of the earlier work in polyamine chemistry
nicely explained by a preliminary deprotonation of the focused on chelate formation, there is now a growing interest
NH2 ligand. These include base hydrolysis (equation 7), in the use of more rigid amine ligands to produce geometric
NH ND exchange,22 s-NH racemization, and some N C clusters153157 (see Self-assembled Inorganic Architectures).
bond formation reactions (equation 12). In every case, the rate Such arrangements include triangles,158 squares,159 cubes,
of the reaction is proportional to the OH concentration and, tetrahedra, boxes, ladders, and helicates.160,161 The strategy
as mentioned earlier (see Section 1), in favorable cases the is based, not only on the ligand design, but also on
deprotonated species can be isolated and characterized.23,24 the stereochemistry of the coordinated metal ion.157 For
example, using the ligand (244), an M2 L2 cyclic dimer
is formed with AgI (linear N2 geometry) and an M4 L4
n+
cage with PdII (square-planar N4 geometry). With ZnII
NH2
(tetrahedral) and CoII (octahedral), one-dimensional zigzag
Co2+ + en + O2 H2N NH2CH2CH2NH2
chains and infinite one-dimensional polymacrocyclic networks
Co
H2N X are formed respectively.162
NH2
O2
HN N N NH
2+ n+
NH2 NH2
H2N NH2 Cl H2N NH2CH2CH O
Co (244)
Co
H2N Cl H2N X
N NH2
To construct a tetrahedral M4 L6 cluster, four octahedral
metal centers with threefold symmetry and six rigid bis-
Figure 7 Imine formation bidentate ligands of twofold symmetry are needed. (An M2 L3
24 AMMONIA & N-DONOR LIGANDS
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Chemistry, ed. G. Wilkinson, Pergamon Press, Oxford, 1987, J. C. Huffman, D. N. Hendrickson, and G. Christou, Inorg.
Chem., 2002, 41, 2441.
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132. D. A. Buckingham, W. G. Jackson, P. A. Marzilli, and
106. A. N. Golub, H. Kohler, and V. V. Skopenko eds, Chemistry
A. M. Sargeson, Aust. J. Chem., 1999, 52, 185.
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133. J. M. W. Browne, J. Wikaira, and R. M. Hartshorn, J. Chem.
107. G. A. Lawrance, Adv. Inorg. Chem., 1989, 34, 145.
Soc., Dalton Trans., 2001, 3513.
108. R. W. Hay and F. M. McLaren, Transition Met. Chem., 1999,
134. M. D. Vaira, F. Mani, and P. Stoppioni, Inorg. Chim. Acta,
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109. A. Hazell, C. J. McKenzie, and L. P. Nielsen, Polyhedron,
135. F. V. Rybak-Akimova, A. Y. Nazarenko, L. Chen, P. W.
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Krieger, A. M. Herrera, V. V. Tarasov, and P. D. Robinson,
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136. A. Grohmann and F. Knoch, Inorg. Chem., 1996, 35, 7932.
111. C. W. Tabor and H. Tabor, Ann. Rev. Biochem., 1984, 53, 749.
137. C. Jubert, A. Mohomadou, E. Guillon, and J.-P. Barbier,
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AMMONIA & N-DONOR LIGANDS 27
141. T. Mashiko and D. Dolphin, in Comprehensive Coordination 153. F. Swiegers and T. J. Malefetse, Chem. Rev., 2000, 100, 3483;
Chemistry, ed. G. Wilkinson, Pergamon Press, Oxford, 1987, Coord. Chem. Rev., 2002, 225, 91.
Vol. 2, p. 813. 154. S. Leininger, B. Olenyuk, and P. J. Stang, Chem. Rev., 2000,
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152. D. Yang and D. A. House, Polyhedron, 1983, 2, 1267.
Analytical Chemistry of the element is present, its oxidation state, or its occurrence as a
specific chemical compound. When the element in question is
the Transition Elements not distributed uniformly throughout the matrix, the question
of its location, for example, at a particular site in a solid catalyst
(see Catalysis) or grain boundary (see Grain Boundary) of an
Alan T. Hutton alloy (see Alloys), becomes of special interest.
University of Cape Town, Rondebosch, South Africa Since the analyte is often present in quite a complex matrix
comprising other elements or substances that may or may
Based in part on the article Analytical Chemistry of the Transition not interfere with any projected method of determination, and
Elements by Harry M. N. H. Irving & Alan T. Hutton which appeared
in the Encyclopedia of Inorganic Chemistry, First Edition.
may indeed be quite a minor constituent of the whole sample,
these considerations will effectively dominate the working
details of any analytical procedure. There can therefore be no
1 Introduction 1 case for prescribing a single definitive method for (say) nickel
2 Historical Perspective 2 that would be universally applicable to its determination
3 Pretreatment of the Sample 3 in alloys (see Alloys), organometallic compounds (see
4 Qualitative Analysis 4 Organometallic Complexes), inorganic salts (see Ionic Bonds),
5 Gravimetric Analysis 4
or coordination compounds (see Coordination Complexes),
6 Titrimetric Analysis 5
to its presence as a trace constituent (see Trace Element)
7 Spectrophotometric Analysis 6
in maize or other plant products, or in natural waters
8 Atomic Emission Spectroscopy 6
or effluents.
9 Atomic Absorption Spectroscopy 7
10 X-ray Methods 8 The environmental scientist will often wish to distinguish
11 Activation Analysis 9 between the total mercury in a sample of sea-water and
12 Electrochemical Methods 10 the amounts of methylmercury compounds in it (see Metal
13 Platinum Group Metals (PGMs) 10 Ion Toxicity). Other factors that influence the choice of an
14 References 10 analytical method for a particular element and the details of
procedure stem from the actual reasons for carrying out the
analysis in the first place. Do we need the highest possible
precision and accuracy, as when assessing the purity of gold
and silver or a material for use in semiconductors? Are routine
analyses to be conducted on large numbers of samples of very
1 INTRODUCTION
similar type? Is the desired level of precision one set by the
eventual use of the analytical result purely for quality control?
The analytical chemistry of the transition elements (see Is the speed of obtaining a result of overriding importance, as
Transition Metals), that is, those with partly filled shells of when analyzing the molten contents of a furnace? Or the need
d (see dn Configuration) or f electrons (see f-Block Metals),
to limit the cost of each analytical determination? Or the need
should include that of the first transition period (Sc, Ti,
to use semi-skilled labor? Other factors that affect the choice
V, Cr, Mn, Fe, Co, Ni, and Cu) and that of the second
of analytical method and the details of procedure depend
transition series (Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, and Ag).
on the amount of sample available and perhaps its unique
The third transition series embraces Hf, Ta, W, Re, Os, Ir,
character. These considerations apply with special force to the
Pt, and Au, and although it formally begins with lanthanum,
elemental analysis of archaeological artifacts1 and museum
for historical reasons this element is usually included with
the lanthanoids (rare-earth elements) (see Scandium, Yttrium specimens.2
& the Lanthanides: Inorganic & Coordination Chemistry; For the above reasons it seems appropriate to describe the
Rare Earth Elements). The actinoid elements (see Actinides: methods available for analyzing, in particular, the transition
Inorganic & Coordination Chemistry) are all radioactive metals and to do so in rather broad outline; details of
(see Radioactive Decay) and those with atomic number (see procedure have thus been relegated to representative specialist
Atomic Number) greater than uranium (Z = 92) are artificial; textbooks36 and research publications. Major reference works
the analytical chemistry of these elements is too specialized include the multivolume Treatise on Analytical Chemistry
to consider here. series,7 the ongoing Wilson and Wilsons Comprehensive
Chemical analysis originally sought to determine what Analytical Chemistry series (now up to volume 43),8,9 the
elements were present in a particular sample and their Encyclopedia of Analytical Science (10 volumes),10,11 and the
concentrations, that is, answers to the questions Whats recent Encyclopedia of Analytical Chemistry (15 volumes).12
in it? and How much? were sought. As time went on The latter work provides an outstanding source of information
the questions became more searching and the analyst had to on the theory, instrumentation, and applications of modern
address considerations of speciation, that is, the form in which analytical chemistry.
2 ANALYTICAL CHEMISTRY OF THE TRANSITION ELEMENTS
2 HISTORICAL PERSPECTIVE even dissolved gold and separated the silver as its insoluble
chloride. By the fourteenth century, cupellation had become a
statutory method for assaying gold, and Charles I of Hungary
2.1 Introduction decreed in 1342 AD that a special laboratory for this purpose
(domus regalis) should be set up in every mining town.13
As soon as chemical substances of plant or mineral origin
However, problems arising from unreliable analysis did not
became the objects of commerce, the need for what we
go away so easily and even in the nineteenth century astute
nowadays think of as quality control became evident, for
dealers in France found that they could make a tidy profit by
the realities of human nature soon ensured that problems of
buying silver with a low assay from some laboratories and
adulteration, false weights, and even plain deception had to
selling it elsewhere where they knew they could receive a
be taken into account. Thus, Pliny (23 79 AD) recorded that
high assay. In 1829 the embarrassed administration sought
the adulteration of copper sulfate by iron sulfate could be
for a solution by offering a prize for a simple and rapid
detected by testing a solution with a strip of papyrus soaked
method of analysis with an error of less than 4 to 5 parts in
in gall-nuts, which blackened if iron was present.
104 that could be universally accepted. Joseph Gay-Lussac
In the absence of mineral acids only dry methods could
was the successful prizewinner with his method of adding a
be employed to detect fraud or defeat the counterfeiters, who
standard solution of sodium chloride to a solution of the silver
became active from the very early days of jewellery and
in nitric acid until one drop of the dilute standard solution no
precious vessels of gold and silver. In the earliest references
longer produced further turbidity due to the precipitation of
to fire assay, found in cuneiform tablets, the King of Babylon
silver chloride. With minor improvements for detecting the
complained to the Egyptian Pharaoh Amenophis IV (reigned
endpoint, this simple method is still in use 175 years later.13
1375 1350 BC), Your Majesty did not look at the gold which
During the fifteenth century the metals zinc, antimony,
was sent me last time . . . after putting them in the furnace
bismuth, and probably cobalt were discovered, together with
this gold was less than its weight. The Bible contains many
many new reactions now used in quantitative analysis.13,14
references to fire assaying, for example, As the fining pot
For example, A. Libavius (1540 1616) noted how ammonia
for silver, and the furnace for gold; so is a man to his praise
in water could be determined by the blue color formed with
(Prov. 27, 21); . . . for he is like a refiners fire, . . . and he shall
a copper salt. Robert Boyle (1627 1691) was the first to use
purify the sons of Levi, and purge them as gold and silver
a solution of hydrogen sulfide (which he made from flowers
(Mal. 3, 2 3); As they gather silver, and brass, and iron, and
of sulfur, potash, and ammonium chloride) as an analytical
lead, and tin, into the midst of the furnace, to blow the fire
reagent, and he noted the black precipitate it formed with lead,
upon it, to melt it . . . (Eze. 22, 20); And I will turn my hand
gold, and mercury.
upon thee, and purely purge away thy dross, and take away all
Chemical analysis came into being to meet the demands
thy tin (Isa. 1, 25).13,14
of early technology. The need for metals in the eighteenth
The separation of silver from gold was a difficult task,
century led to the shortage of the wood and charcoal needed
and Pliny refers to an essentially chemical method in which
for smelting iron. Replacing them by coal gave a brittle prod-
the alloy is roasted with iron sulfate and common salt in
uct and it was not until about 1750 that careful analytical
the presence of brick dust, which absorbs the silver chloride
work revealed the reason. More mining exploration led to the
formed and leaves pure gold. However, some 250 years earlier,
discovery of new minerals and produced additional problems
Hieron, King of Syracuse (200 BC), had asked Archimedes to
for the analysts who had to devise new qualitative and quanti-
examine the composition of a new golden crown that he
tative methods, particularly in those countries with the richest
suspected might have been made from a gold silver alloy.
mineral deposits, and notably in Sweden. M. H. Klaproths
Since the density of gold (19.3) is nearly twice that of silver
contributions (1743 1817) in Germany were especially note-
(10.5) the composition of the crown was easily determined
worthy, for he originated the technique of alkali fusion for
by a purely physical method, probably the first use of a
opening up minerals and used silver or gold vessels for the
nondestructive method in analysis.
purpose. He realized that foreign materials could be introduced
The process of fire assay is essentially quantitative in the
into his samples when they were finely ground in a mortar and
sense that it concerns a change in weight before and after some
he made appropriate corrections. He made significant advances
heat treatment. The essential balance was a familiar piece of
in the analysis of mixtures of iron, manganese, aluminum, and
equipment employed by generations of traders, as evidenced
chromium in solutions containing phosphates and arsenates.13
by the fact that weights used in Babylon in 2600 BC are still
in existence.
The process of assaying gold was current from early times 2.2 Blowpipe Methods
and in the thirteenth century it was clearly described in the
Summa perfectionis magisterii (ascribed to Geber). This also An important technique developed in the mid-eighteenth
described the preparation of aqua fortis (nitric acid), which was century was to miniaturize large-scale metallurgical operations
known to dissolve silver but not gold, and aqua regia, prepared by adapting the blowpipe, which had long been used by
from a mixture of nitric acid with ammonium chloride, which glassblowers and goldsmiths, to provide an indispensable
ANALYTICAL CHEMISTRY OF THE TRANSITION ELEMENTS 3
adjunct for the examination of minerals in the laboratory and fluorescence (T. S. West, 1966) and X-ray fluorescence
especially in the field. In the hands of Gahn and Cronstedt in the (XRF) (1923) (see Section 10.1), and optical absorption spec-
eighteenth century it became a simple instrument for directing trophotometry (ca. 1940) (see Section 7) gained increasing
a fine and concentrated flame into a small portion of the importance as the relevant apparatus became more refined and
powdered sample in a hollowed-out block of charcoal. With commercially available.14 Although radiochemical methods
the aid of fluxes such as borax, soda, and sodium ammonium began to be exploited from the early years of the last century,
phosphate (microcosmic salt), many metal oxides could be a new and major analytical technique, that of neutron activa-
reduced and valuable information gained from the color and tion analysis (see Section 11.1), had to await the availability
reactions of the bead that remained. Bergmann was a great of nuclear reactors as neutron sources, following the stimulus
exponent of this technique and his book De tubo feruminatorio of the Second World War. This also provided the stimulus
(1779) summarized all the knowledge of his time. J. J. for many analytical procedures based on liquid liquid extrac-
Berzelius disseminated it widely through his book Abhandlung tion (or solvent extraction), although its potential had been
om Blasrorets awendende i kemien och mineralogien realized as early as the beginning of the twentieth century.14
(1820) and its translations into many European languages.
This technique, which was once a stable feature of every
course on qualitative analysis, fell into disuse around 1910.14
3 PRETREATMENT OF THE SAMPLE
2.3 Titrimetry and Gravimetry
When the desired element is present in the sample at quite
At first, quantitative analysis by titrimetry was confined a low concentration, it may be necessary to take a large
to such problems as measuring the strength of vinegar amount for analysis and this raises the important question of
and the basic articles of commerce such as sulfuric acid, securing a truly representative sample if the initial material
hydrochloric acid, and solutions of chlorine in water. Thus, is not homogeneous.17 An aliquot portion of a solution can
the amount of alkali in pearl ash was arrived at by measuring be obtained with suitable accuracy, but this does not solve
the number of teaspoonfuls of a dilute solution of nitric the problem of how to obtain a homogeneous solution of
acid needed before effervescence ceased; detection of the the original specimen without introducing large amounts of
endpoint by a change in the color of litmus was a later reagents that cannot readily be removed and may complicate
improvement by William Lewis (1767). Titrimetry took the subsequent procedures. The rate of dissolution is always
a step forward when F. A. H. Descroizilles (1757 1825) increased if the sample to be analyzed is presented in the form
introduced the first form of burette and a crude standard of a fine powder and such comminution has been achieved
flask described as a small jug . . . in the neck of which by a variety of techniques contrived to disperse the specimen
a mark is made with a diamond indicating the place up without contamination by the equipment, vessels, or reagents
to which the vessel contains just 2 dl.1315 In about 1846, used.3,4
F. Margueritte introduced potassium permanganate for the Although fusion with alkaline or acidic fluxes such as
titration of iron and Pennys process (1850) extended this with KHF2 , K2 S2 O5 , or Na2 CO3 (with or without KNO3 ) is
a standard solution of potassium chromate since permanganate usually effective, it may introduce materials that subsequently
could not be used when the iron was taken into solution produce complications. HNO3 and HF are often used for
with hydrochloric acid.16 Later developments in titrimetry Zr, Hf, Ta, Nb, Ti, and other metals, refractory oxides
centered around the use of electrochemical methods, these (see Oxides: Solid-state Chemistry), borides (see Borides:
being especially useful for detecting the endpoint since they Solid-state Chemistry), carbides, and nitrides (see Nitrides:
could be adapted to recording devices and automatic control.14 Transition Metal Solid-state Chemistry). The removal of
Complexometric titrations (see Section 6.3) for many metals unwanted material, especially organic matter, by dry- or wet-
date from G. Schwarzenbachs work in the early 1940s. ashing demands special care, as unacceptable losses of certain
Classical analysis by gravimetry (see Section 5) took a elements may arise from these processes.18 For voltammetric
new turn when L. H. Tschugaeff reported the novel use analyses, where the analyte must be in an ionic form, organic
of a new organic reagent, dimethylglyoxime, in 1905, but material must be removed completely, as well as interfering
several decades passed before other reagents such as cupferron substances such as oxygen, hydrogen peroxide, complexing
(see Cupferron), 8-hydroxyquinoline, 1-nitroso-2-naphthol, agents, surfactants, and any substances that might be adsorbed
the alkyl- and arylarsonic acids, and so on, became firmly on the electrode surfaces.
established.14,15 The modern trend has been to carry out digestions in closed
vessels of quartz using suitable mineral acids (HNO3 , HCl,
2.4 Physical Methods H2 SO4 , or HClO4 ) or in glassy carbon or Teflon-lined bombs
(for HF). The digestions are often carried out under high
Physical methods such as spectroscopy (1925), atomic pressure (up to 30 bar) and high temperature (up to 320 C).
absorption (A. Walsh, 1955) (see Section 9), atomic Microwave heating is increasingly used to speed the process
4 ANALYTICAL CHEMISTRY OF THE TRANSITION ELEMENTS
and avoid any possible contamination from flames or other organic reagents, it became feasible to precipitate a desired
heat sources.19 In a modern UV digestor, samples containing element as a metal coordination compound (see Coordination
a small volume of pure hydrogen peroxide are arranged in Complexes) that often had a low solubility and a favorably
stoppered quartz vessels around a high-pressure mercury- high equivalent weight.24 Organic precipitating reagents are
vapor lamp which generates OH radicals that degrade organic generally bidentate (see Bidentate Ligand) chelating ligands
matter. A typical digestion of an hour or less at 90 C is used (see Chelating Ligands), with O, N, and S being the most
in the determination of Ni (1 g dm3 ) or Cu (30 g dm3 ) commonly encountered donor atoms (see Donor Atom). At
in lake water or municipal waste water. first it was hoped that it would be possible to synthesize a
reagent specific for each element, thus obviating the need
for elaborate separation procedures. This now seems to have
been an impossible goal and the best that can be achieved
4 QUALITATIVE ANALYSIS is provision of a reagent which, under carefully specified
reaction conditions (e.g. control of pH and the presence of
The discovery of so many elements up to the beginning certain auxiliary complexing agents), shows a high selectivity.
of the twentieth century led to innumerable schemes for their There appears to be no specific and quantitative precipitant
qualitative analysis, with special regard to the circumstances for scandium, the first of the transition metals. The principal
that frequently occurred in complex mixtures, so that some difficulty is that of separating scandium from the other
degree of separation was mandatory. Contemporary advances metals, since it occurs in practically all yttrium and
in analytical methods have made much of this work of lanthanum minerals, in smaller amounts in tin, tungsten,
historical or pedagogical interest only.20 zirconium, beryllium, titanium, and niobium minerals, and
Immense effort was at one time devoted to devising spot- in minute amounts in almost all rocks. Many of the classical
tests to enable a specific element or chemical group to be gravimetric procedures depend on the precipitation of its
identified in a minute amount of analyte.21 With the advent hydroxide or oxalate and subsequent ignition to Sc2 O3 , which
of techniques that permit of the simultaneous identification unfortunately has a high gravimetric factor. If interfering
of the components of a complex mixture, these too are less elements are first removed, it gives a precipitate with oxine
widely used except in special circumstances.
NO
H3C N OH
C OH
5 GRAVIMETRIC ANALYSIS C
H3C N OH
(a) (b)
5.1 Classical Gravimetry
(8-hydroxyquinoline) from a buffered acetate solution at pH determined titrimetrically. Molybdenum and tungsten have
6.5 8.5 of composition Sc(C9 H6 NO)3 C9 H7 NO (Mr 622.7) been determined similarly by measuring the calcium content
having a low gravimetric factor.25 of precipitated CaMoO4 and CaWO4 .26,28
Gravimetric methods for other transition metals are detailed
by several authors in reference texts;3,4,24,26,27 a representative
selection of well-known organic reagents and their common 6.3 Complexometric Titrations
analytes is given in Figure 1.
A titrimetric procedure for the determination of most of the
transition metals using a common titrant could obviously be of
considerable value. This possibility arose from the pioneering
work of G. Schwarzenbach in 1945.29
6 TITRIMETRIC ANALYSIS If we consider the determination of a transition metal M by
the reaction M + L ML (where L is an organic ligand (see
Ligand) and the charges on the various species are omitted
6.1 Advantages of Titrimetry
in the interests of generality), a successful analytical method
Whereas in gravimetric analysis a reagent is added in must meet the following requirements: (i) the reaction must
excess to a solution of the analyte and the resulting precipitate be sufficiently fast; (ii) it should lead stoichiometrically to
is collected, washed, dried, and weighed, in titrimetry a single product ML without any intermediate reactions or
(formerly volumetric analysis) a reagent of precisely by-products; (iii) there should be a large increase in free
known concentration is added to the test solution in just energy (see Gibbs Energy), so that the reaction is effectively
sufficient amount as to be stoichiometrically equivalent to complete, that is, the stability constant (see Stability Constants
the amount of analyte. No excess is used and the endpoint & their Determination) KML must be large;30 (iv) the ligand
is detected visually (by a change in color or fluorescence L must be readily available and give stable standard solutions;
(see Fluorescence) of a suitable indicator) or instrumentally and (v) there must be some simple means of monitoring the
(e.g. photometrically or by some electrochemical method). course of the reaction, that is, for following changes in the
Titrimetric methods are intrinsically quicker than gravimetric concentration [M] or [ML]. These conditions are generally
procedures and demand less operator skill. The whole met if L is the conjugate base of an aminopolycarboxylic acid
procedure can be automated, conducted on a small scale such as ethylenediaminetetraacetic acid (EDTA, H4 Y), which
(with volumes down to a few microliters), and adapted is known to form very stable 1:1 complexes with a large
to work with highly radioactive materials (see Radioactive number of metals (Table 1) by coordinating to the central
Decay).3,4,28 metal atom through its nitrogen and oxygen atoms to give
up to five chelate rings (see Chelating Ligands) of optimum
size (five atoms).27 The structure of a representative transition
6.2 Individual Determinations metal EDTA complex is illustrated in Figure 2.
The pure salt Na2 H2 Y2H2 O is commercially available; concentration of solutions that absorb in the visible or UV
it is readily soluble in water and its high molecular weight regions (see UV Visible Spectroscopy). Since values of A
(372.16) facilitates the preparation of standard solutions that are additive, procedures are readily found for evaluating the
keep extremely well in hard glass, borosilicate (Pyrex), or composition of mixtures provided there is no interaction
polythene containers, although they are aggressive toward between the molecules.3234
soft glass.29 Complexation proceeds rapidly except in the case The absorption coefficients of the transition metal cations
of CrIII . A few cations tend to form polynuclear complexes themselves are seldom large enough to permit a satisfac-
in alkaline solution and react sluggishly with EDTA at room tory spectrophotometric (absorptiometric) determination, but
temperature; several problems are overcome by heating with complexation of copper with amines (see Ammonia & N-
a known excess of EDTA, then adjusting the pH and back- donor Ligands) (blue color) or iron(III) with thiocyanate (red
titrating. The endpoint is detected visually with a variety color) has long been exploited. Innumerable organic com-
of metallochromic indicators, which change color when [M] pounds have been found to give coordination compounds
decreases to a small value, or electrochemically with, for of high values and 2,2 -bipyridyl, 1,10-phenanthroline and
example, a mercury drop or amalgamated gold foil electrode. 2,4,6-tris(2 -pyridyl)-1,3,5-triazine and their derivatives (see
Titrimetric methods have been proposed for all the metals Ammonia & N-donor Ligands) are of special value in the
listed in Table 1. For example, plutonium can be determined determination of iron(II). Bathocuproine (2,4-dimethyl-4,7-
by complexation with excess EDTA at pH 2.5 and the diphenyl-1,10-phenanthroline) is a very sensitive and selective
excess back-titrated with ThIV using Alizarin S as indicator. reagent for determining copper(I) in the presence of consider-
Molybdenum and tungsten are determinable through the able amounts of iron since for steric reasons (see Steric Effect)
calcium content of CaMoO4 and CaWO4 , and chromium it does not coordinate to FeII .27
through the lead content of PbCrO4 or other means. Good 1,5-Diphenylthiocarbazone (dithizone) forms intensely
methods are available for all the lanthanoids, and although no colored complexes with, for example, Mn, Fe, Co, Ni,
really satisfactory method has been established for gold and Cu, Zn, Pd, Ag, Cd, Pt, Au, and Hg, which are soluble
the individual platinum group metals (PGMs), silver is readily in CCl4 and CHCl3 , a property which facilitates their
obtained in terms of the nickel ion displaced in the reaction separation and individual determination.35,36 Solutions of most
2Ag+ + K2 [Ni(CN)4 ] 2K[Ag(CN)2 ] + Ni2+ .28,29,31 metal dithizonates in organic solvents have the interesting
property of being photochromic (see Photochromism), and
the relatively long half-life of the photoexcited mercury(II)
dithizonate complexes (t1/2 ca. 1 min) has facilitated their
7 SPECTROPHOTOMETRIC ANALYSIS investigation by conventional spectroscopic techniques.37
for qualitative and quantitative analyses, especially for qual- with sample and standards being excited under precisely the
ity control in industry and for research purposes, developed same conditions.6,38
with the growing demands of analytical chemistry and the
availability of more efficient and sophisticated instrumenta-
8.2 Inductively Coupled Plasma (ICP) Sources
tion. The source of excitation transforms the sample into a
plasma of atoms, ions, and molecular radicals that can be Since 1974, the inductively coupled plasma (ICP) torch
excited electronically (see Excited State). The decay of these has become commercially available and is among the most
excited species (see Electronic Transition) involves radiation effective sources for emission spectroscopy in use today. An
of light quanta which can be sorted by wavelength in a suitably ICP discharge is produced by the effect of a radio frequency
designed spectrometer, and this emission spectrum, recorded field (typically 27 to 40 MHz), which creates a magnetic field
in the early days photographically, is now digitally captured inside a stream of argon which is first made conducting by a
using photomultiplier tubes or diode arrays. pilot electric spark, arc or Tesla discharge. A spectrally intense
Excitation by flame is less effective than by electric arc plasma at a temperature of 9000 to 10 000 K is obtained in
or spark, glow, or plasma discharge, or by lasers which the annulus of an ICP discharge operating at 1 2 kW input
produce a more line-rich spectrum; on the other hand, these power. Samples are introduced as powders, gases, or liquids
advantages can only be exploited by instruments capable of using the type of spray chamber already made available in
higher resolution.6 flame spectroscopy.6 Because of the inert atmosphere of the
ICP discharge, some of the difficulties encountered in flame
excitation are avoided: for example, the air acetylene flame
8.1 Arc and Spark Excitation
favors the formation of neutral atoms, while the very hot
One of the most convenient sources of excitation is the low nitrous oxide acetylene flame contains high concentrations
voltage (10 150 V d.c.), high current (1 35 A) discharge of CN and NH species and produces a strongly reducing
between two electrodes. The finely powdered sample is atmosphere. Chemical interferences of this kind, leading to the
contained in a cup machined from a pure graphite rod formation of stable compounds in flames, are almost negligible
(usually the anode) and a pointed graphite rod forms the in the ICP discharge and spectra arising from molecular species
counter electrode. When the arc is struck, the temperature such as CN are minimized. Simultaneous determination of as
of the conducting channels between the electrodes ranges many as 35 elements in a single sample can be carried out
between 4000 and 7000 K and although the emission lines without modifying the conditions for each element: less than
for any given element appear simultaneously, the elements 5 cm3 of sample solution is generally required. Detection limits
in a sample matrix do not vaporize at the same rate and are generally in the range 0.02 2 ppb (ppb = 107 %).39,40
various factors determine their sequential emission. In some
techniques the separation of a volatile element from others less
volatile is deliberately enhanced (e.g. when determining trace
impurities in uranium) by the addition of such substances 9 ATOMIC ABSORPTION SPECTROSCOPY
as silver chloride (carrier distillation method). In other
applications the arc temperature is stabilized to promote The Maxwell Boltzmann distribution law shows that the
uniform and simultaneous evaporation by mixing the sample ratio of the number of atoms Nu in an excited upper state (see
with a spectrochemical buffer such as lithium carbonate, which Excited State) to the number in the ground state No increases
supplies the arc with a constant supply of ions and electrons. exponentially with temperature. For example, the ratio Nu /No
Detection limits for some typical elements range from 0.1 to for Cs (resonance line at 852.1 nm), Ca (422.7 nm), and
1.0% for Nb, Ta, and W, from 0.01 to 0.1% for Bi, Cd, La, Y, Zn (213.8 nm) increases from 4.44 104 , 1.21 107 , and
Zn, and Zr, from 0.001 to 0.01% for Au, Fe, Ir, Mo, and Sn, 7.29 1015 at 2000 K to 2.98 102 , 6.04 104 , and
and from as little as 0.0001 to 0.001% for Ag, Co, Cr, Cu, Ni, 1.48 106 at 4000 K. Even so, this means that for many
Os, Pd, Pt, Rh, and Ru.6,38 transition metals only a small fraction of the vaporized atoms
With high (1000 V) or medium voltages, events occur very are in an excited state capable of emitting a line spectrum,
rapidly in spark discharges. The spectra depend not only even at the temperature of an ICP.
on the physical conditions of operating but on that part of In 1955, A. Walsh41 recognized this and showed how
the spark gap actually viewed by the spectrograph and also the absorption from the great preponderance of unexcited
on the selected time interval during the discharge. Owing molecules could be exploited analytically.4244 Thus, in atomic
to such factors and purely matrix effects which affect the absorption spectroscopy (AAS) the light from a (usually
absolute intensity of lines emitted by elements in a sample, modulated) source emitting the spectrum of the desired analyte
quantitative measurements normally involve a comparison of element is passed through a sample atomization cell (such
the spectra of the analytical sample with those of artificial as a flame or graphite tube furnace), a monochromator (to
standards containing the desired elements at comparable isolate the desired source emission line) and finally into a
concentrations in as closely a similar matrix as possible, detector to allow measurement of the change in source line
8 ANALYTICAL CHEMISTRY OF THE TRANSITION ELEMENTS
intensity due to absorption by sample atoms. The narrow wine the samples are commonly mineralized by incineration or
waveband (0.001 0.005 nm) light source is usually a hollow by wet-ashing with acids. In metals and alloys these elements
cathode discharge lamp prepared with the desired element, are frequently present in somewhat higher concentrations and
although some multielement lamps are now available. In the these materials may, therefore, be analyzed directly after
sample atomization cell a fraction of light from the essentially dissolution in appropriate acids.
monochromatic source is absorbed by atoms from the sample, The ferrous metals, which include Co, Ni, Cr, Mn, and Mo,
which is sprayed as a solution into the flame by a pneumatic besides Fe, all have line-rich spectra and with the exception
nebulizer, or vaporized electrothermally from a solid in a of iron all are used as alloying elements in steels. No specific
graphite furnace. The amount of radiation remaining can then interference effects have been observed for Fe, Co, or Ni;
be monitored, the concentration of atoms in the path of the light for Cr and Mn the effects are only slight; for Mo they
beam being determined by Beers law. Calibration is achieved can be considerable. The tendency to exhibit interference
with standard solutions containing known concentrations of effects corresponds to the tendency to form oxides in the
the element being determined. flame and is, therefore, predominantly due to the formation
In the case of flame atomization, fuel oxidant mixtures like of nonvolatile compounds and may be eliminated by using
acetylene air are used for most easily atomized elements; for releasing elements. Thus, for example, the depressive effect
the less easily atomized elements, for example, those that of Si on Cr and Mn may be eliminated by the addition of Ca
exist mainly as monoxides, the analytical sensitivity can be or Sr to the solution sprayed.
greatly enhanced by going to a higher-temperature flame, The sensitivity of AAS is usually sufficient to allow
such as acetylene nitrous oxide, thus shifting the equilibrium determination of these elements in steels after simply
M+O MO toward the metal. dissolving the sample. Most often a mixture of hydrochloric
The development of nonflame atomization systems, and nitric acids is used, but sometimes sulfuric and phosphoric
particularly the graphite tube furnaces, resulted in a significant acids with several drops of nitric acid to facilitate oxidation are
improvement in the analytical sensitivity for many elements.45 preferred. In any case, the volumes of acids in all the solutions
While the flame-based technique is capable of measuring sprayed must be kept constant, because generally the acids
sample concentrations down to 100 ng cm3 (parts per billion), have a depressive effect. For the analysis of organic materials,
graphite furnace devices offer detection limits of the order plants, fertilizers, and so on, the ash is often digested with
of 0.1 ng cm3 , a 1000-fold gain. These devices consist of acids and the undissolved residue filtered off.
a graphite tube, into which a small amount of sample is A special group of materials analyzed are crude and
placed, which is then heated electrically to a high temperature, lubricating oils. Ni, V, and Fe act as poisons on cracking
vaporizing and atomizing the sample. They are particularly catalysts (see Catalysis), and the wear of mechanical parts
useful when the amount of sample available is limited, of engines can be indicated by the content of trace elements
since sample volumes are usually in the microliter range. (see Trace Element) in lubricating oils. Their determination
Unfortunately, these devices often suffer from matrix effects is therefore an important task. To eliminate the tedious
and exhibit relatively poor precision because of the small mineralization of the samples, they can be analyzed directly
sample size. However, a typical detection limit for many after dilution with some nonpolar solvent, usually xylene, or
elements using furnace AAS is 1013 g. methyl isobutyl ketone (MIBK).
In general, as an analytical technique for trace metal Among the noble metals, Au and Pd are most easily
(see Trace Element) determinations, AAS has important accessible to AAS determinations. Both are easily atomized
advantages. It has high sensitivity for many elements, with
in the flame and are not subject to any specific interference
perhaps 60 or so elements measurable with flame atomization
effects, so that their determination is sensitive and without
in the ppm range (0.1 10 g cm3 , or 107 105 g on
complications. Pt, Rh, Ru, Ir, and Os may be determined,
an absolute basis), and more than half of these measurable at
but with several specific interference effects, especially in
significantly lower concentrations with nonflame atomization.
low-temperature flames.
In addition it is simple, rapid, and relatively low cost and can
be highly specific, exhibiting few interferences.
Table 2 Estimated sensitivity of neutron activation analysis51 and then plotting the current potential curve of the stripping
voltammogram (anodic stripping voltammetry, ASV).57
Sensitivity (g) Element
1 1012 Dy, Eu
5 1012 Au, Ho, Lu
1 1011 In, Mn, Re, Sn 13 PLATINUM GROUP METALS (PGMs)
5 1011 As, Kr, La, Pr, Sc, Tb, Tu, W, Yb
1 1010 Sb, Br, Cu, Er, Ga, Pd, Na, Ta, Yt
5 1010 Al, Cs, Co, Gd, Hf, Nd, Li(n,), P, Rb Owing to great similarities in chemical properties and
1 109 Ba, B(n,), Cd, Ce, Hg, Os, Pt, K, Ru their association together in Nature, the second and third
5 109 Cl, Ge, I, Ag, Te, Th, Sn, U, Xe, Zn triads of groups 8 10 of the periodic table (Ru, Rh, Pd
1 108 Mo, Ni, Si, Th
and Os, Ir, Pt) present many difficulties for the analyst.
5 108 Bi, Se
1 107 Cr, Fe, Sr, Zr Their comparative rarity and intrinsic value demand their
5 107 Ca, S recovery from spent catalytic converters in the petroleum and
many other chemical industries, from the increasing number
of pollution control units in motor vehicles, from scrapped
jewellery and the scrap of the electronics industry, as well as
which gives better discrimination between similar elements
material from geochemical exploration, the exploitation from
and is particularly suited for the simultaneous determination
mineral deposits, and sweeps. The first requirement is to
of a large number of elements in many varied specimens.
collect a homogeneous alloy (see Alloys).58,59
Disadvantages of charged particle methods are the low flux of
Often a friable alloy can be produced simply by melting
particles and the small penetration depth.
with aluminum; this can then be ground into a powder.
Collection by fire-assay methods involving the use of tin and
iron nickel copper alloys has been extensively studied and
collection by melting with nickel sulfide, copper sulfide, and
12 ELECTROCHEMICAL METHODS copper alone has its advocates. Lead oxide, as used in the fire
assay of gold and silver, is less suitable for isolating platinum
and palladium and still less so for rhodium, ruthenium, and
There is a whole gamut of electrochemical methods
iridium, while osmium is largely volatile in the cupellation
available for the determination of the transition elements.55
stage. The optimum procedure is naturally highly dependent
Electrogravimetric methods are available for large numbers
on the nature of the sample and in many cases some form of
of metals (e.g. Cu, Ag, Cd, Co, Ni, Sn, Zn, Pb, and Tl)
acid digestion is preferable.58,59
provided these are available in weighable amounts. Controlled
With modern instrumentation it is often possible to make
potential electrolysis at a mercury pool electrode is best
determinations of individual elements without the necessity
suited for separations (e.g. Cu, Cd, and Pd from uranium) or
for any chemical separations, but while mutual interferences
removing traces of metallic impurities when preparing very
for AAS and ICP emission spectrometry are often small
pure electrolytes for use in polarography.6
the sensitivity, for example, for iridium, may be unacceptably
Polarography (discovered by Jaroslav Heyrovsky in
low and chemical separations are required.60 The separation of
1922)56 is a technique in which the potential between a
rhodium from iridium is one of the most challenging analytical
dropping mercury electrode and a reference electrode is slowly
tasks. Ruthenium and osmium are most commonly separated
increased at a rate of about 50 200 mV min1 while the
from other PGMs and matrix elements by distillation of their
resultant current (carried through an auxiliary electrode) is
tetroxides.59
monitored; the reduction of metal ions at the mercury cathode
Separation of PGMs by solvent extraction or using cation
gives a diffusion current proportional to the concentration
exchangers (see Ion Exchange) is well documented58,59 and
of the metal ions. The method is especially valuable for the
gravimetric and titrimetric methods are prominent, especially
determination of transition metals such as Cr, Mn, Fe, Co,
in the older monographs.61 The most important instrumental
Ni, Cu, Zn, Ti, Mo, W, V, and Pt, and less than 1 cm3 of
techniques include emission spectroscopy, XRF, AAS, and,
analyte solution may be used. The detection limit is usually
of course, the use of activation analysis (see Section 11).58,59
about 5 106 M, but with certain modifications in the basic
technique, such as pulse polarography, differential pulse
polarography, and square-wave voltammetry, lower limits
down to 108 M can be achieved.
Especially for those metals that form amalgams (e.g. Cu, 14 REFERENCES
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ANALYTICAL CHEMISTRY OF THE TRANSITION ELEMENTS 11
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38. K. Slickers, Automatic Atomic Emission Spectroscopy, 53. S. Amiel ed., Nondestructive Activation Analysis, Elsevier,
2nd edn., Bruhlsche Universitatsdruckerei, Giessen, D-35334 Amsterdam, 1981.
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39. A. Montaser and D. W. Golightly, Inductively Coupled Particle-induced X-Ray Emission Spectroscopy (PIXE), John
Plasmas in Analytical Atomic Spectroscopy, VCH, Weinheim, Wiley & Sons, Chichester, 1995.
1987. 55. A. J. Bard and L. R. Faulkner, Electrochemical Methods:
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Techniques in Inductively Coupled Plasma Optical Emission New York, 2001.
Spectrometry, 2nd edn., Perkin-Elmer, Norwalk, CT, 1997. 56. A. M. Bond, Modern Polarographic Methods in Analytical
41. A. Walsh, Spectrochim. Acta., 1955, 7, 108. Chemistry, Marcel Dekker, New York, 1980.
42. A. Walsh, Anal. Chem., 1991, 63, 933A. 57. P. T. Kissinger and W. R. Heineman eds., Laboratory
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Dekker, New York, 1996.
44. W. Slavin, Anal. Chem., 1991, 63, 1033A.
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45. B. V. Lvov, Anal. Chem., 1991, 63, 924A.
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46. B. Welz and M. Sperling, Atomic Absorption Spectrometry,
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nd ed. E. L. Grove, Plenum Press, New York and London, 1978,
47. B. K. Agarwal, X-ray Spectroscopy, 2 edn., Springer-
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61. F. E. Beamish and J. C. Van Loon, Recent Advances in the
48. J. I. Goldstein, D. E. Newbury, P. Echlin, and D. C. Joy,
Analytical Chemistry of the Noble Metals, Pergamon Press,
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49. T. L. Barr, Modern ESCA: The Principles and Practice of Acknowledgment
X-ray Photoelectron Spectroscopy, CRC Press, Boca Raton,
FL, 1994. In revising and updating our original article from the
50. R. E. Van Grieken and A. A. Markowics eds., Handbook first edition of the Encyclopedia of Inorganic Chemistry,
of X-ray Spectrometry, Marcel Dekker, New York, I have tried to preserve the clear, inimitable style of the
1993. late Harry Irvings writing, particularly in the historical
overview presented, and have attempted to retain his insightful
51. T. B. Pierce, Sel. Annu. Rev. Anal. Sci., 1971, 1, 133.
perspectives throughout the article. Ten years after his death,
52. Z. B. Alfassi ed., Activation Analysis, CRC Press, Boca this article is dedicated to his memory.
Raton, FL, 1990.
Antimony: Inorganic concentrate directly with scrap iron to give elemental antimony
(equation 1), which can be purified by melting with sodium
nitrate and sodium carbonate.1
Chemistry
Sb2 S3 + 3Fe 2Sb + 3FeS (1)
Hans Joachim Breunig
University of Bremen, Bremen, Germany More complex antimony ores can be treated by leaching
with alkali hydroxide or sulfide and by electrolysis of
Based in part on the article Antimony: Inorganic Chemistry by the resulting solution of sodium thioantimonate, Na3 SbS4 .
R. Bruce King which appeared in the Encyclopedia of Inorganic Elemental antimony can also be recovered from the flue dust
Chemistry, First Edition.
of lead smelters.
The dominant use of antimony is as an alloying element
1 Introduction 1 to harden lead, notably for grids in motor car batteries.1
2 Antimony Hydrides 2 PbSb alloys have also been used for ammunition or for
3 Antimonides 2 movable types in printing presses.1 Antimony is a component
4 Antimony Group 13 Metal (Al, Ga, In) and Group of many bearing alloys, like Babitt metal (an alloy of antimony,
15 Metal (Si, Ge, Sn, Pb) Compounds 3 tin, copper, and other metals), which are useful as bearings
5 Antimony Pnicogen (N, P) Compounds 3 because they are soft and slippery. Sb2 O3 can be applied
6 Antimony Chalcogen (O, S, Se, Te) Compounds 3 in chemicals used to impregnate plastics, textiles, rubber,
7 Antimony Halides 5 and other materials as a flame retardant. The orange red
8 Transition-metal Complexes with Sbn Ligands 6 form of Sb2 S3 , which is obtained from Sb(III) and H2 S,
9 References 7 has been used for pyrotechnical articles and as a pigment
in paints, plastics, or rubber. An important medicinal use of
antimony compounds is the treatment of tropical diseases
caused by parasites like leishmaniasis or bilharziasis.2,3
Therapies include potassium antimony(III) tartrate, sodium
antimony(V) gluconate (Pentostam ) or N -methyl-glucamine
1 INTRODUCTION antimonate(V) (Glucantime ). Proposed structures are shown
in Schemes 1 and 3. It is thought that Sb(V) is reduced to
Sb(III) in vivo. Potassium antimony(III) tartrate (tartar emetic)
1.1 History, Occurrence, Use, and Isotopes is an emeticum. It is also used in the therapy of infections in
Antimony compounds were known to the ancients. In veterinary medicine.
Egypt and other ancient oriental cultures, Sb2 S3 (stibnite) was Natural antimony consists of the isotopes 121 Sb (57.3%)
used as medicine and for cosmetic purposes, for example, and 123 Sb (42.7%). Important artificial isotopes include
as a component of black eye makeup. The names of the
122
Sb (1/2 = 2.8 days), 124 Sb (1/2 = 60.4 days), and 125 Sb
element in different languages originate from the Latin words (1/2 = 2.7 years).
stibium and antimonium. The former was used in 50 BC by
Pliny for Sb2 S3 . It is probably of Egyptian origin. For the 1.2 Elemental Antimony
word antimonium, there are several more or less fantastic
etymologies (against the monks, against loneliness etc.). The form of elemental antimony that is stable at normal
Probably it is a retranslation of the Arabic word for stibium temperatures and pressures is the gray, metallic rhombohedral
into Medieval Latin. -form, mp 630.7 C, bp 1587 C, density 6.70 g cm3 .
Antimony is among the less abundant elements in the Crystals are lustrous. They have a relatively high electrical
earths crust (0.6 ppm). The most important antimony ore resistivity (41.7 cm at 20 C). The structure of -Sb
is stibnite, which occurs in large quantities in China, South consists of sheets of covalently bonded antimony stacked
Africa, Bolivia, and other countries. Other antimony sulfide in layers, which are formed of puckered six-membered rings.
ores are tetrahedrite (Cu3 Sb2 S3 ), wolfsbergite (CuSbS2 ), and Each antimony forms three shorter bonds (2.91 A) in the same
jamesonite (FePb4 Sb6 S14 ). Weathering of stibnite leads to layer as well as three longer bonds (3.36 A) to antimony
valentinite (Sb2 O3 ). atoms in the adjacent layer. In addition to the -form, other
It is not very difficult to recover stibnite from other minerals allotropes include a very unstable yellow form and black forms
because the melting point of this antimony mineral is low obtained electrolytically or by condensing the vapor on cold
(546 C). Heating in the range of 550 to 600 C results in surfaces. Two crystalline allotropes are made by high-pressure
selective melting of the stibnite, which can be collected as techniques. At 85 kbar, a modification with a primitive cubic
crude concentrate. Roasting in air produces Sb2 O3 that can lattice is formed where each antimony atom is in an octahedral
be reduced with coke. Another method is to reduce the Sb2 S3 environment of six equidistant (2.96 A) neighbors. Further
2 ANTIMONY: INORGANIC CHEMISTRY
Scheme 1
increase in the pressure to 90 kbar gives a hexagonal close- statu nascendi (equation 2), by reaction of Mg3 Sb2 with dilute
packed form with SbSb distances of 3.28 A for the 12 hydrochloric acid, or, at best, by reaction of SbCl3 with NaBH4
nearest neighbors. Thin films of amorphous antimony on (equation 3) in hydrochloric acid.
surfaces of AuSb2 and MoS2 contain crystalline structures
of Sb4 tetrahedra.4 Antimony vapor consists of Sb2 and Sb4 Sb(OH)3 + 6H SbH3 + 3H2 O (2)
molecules. The calculated SbSb bond length in Sb4 tetrahedra
SbCl3 + 3NaBH4 SbH3 + 3NaCl + 3BH3 (3)
is 2.687 A.
Elemental antimony is stable in air and moisture at room
temperature but oxidizes upon heating to give Sb2 O3 , Sb2 O4 , The structure is pyramidal with a HSbH angle of 91.54 ,
and Sb2 O5 . It reacts with Cl2 to give SbCl5 and also reacts and an SbH bond length of 1.70 A.5 SbH3 is an endothermic
with the other halogens and with sulfur. Antimony is not sol- compound (Hf = 145.1 kJ mol1 ) decomposing at room
uble in HCl or dilute H2 SO4 . Hot concentrated H2 SO4 gives temperature to metallic antimony and hydrogen. As a
Sb2 (SO4 )3 and concentrated HNO3 gives hydrated Sb2 O5 . side product of the syntheses of SbH3 , small amounts
of distibine Sb2 H4 were also detected. SbH3 is used
1.3 General Aspects of Antimony Chemistry in Metal Organic Chemical Vapor Deposition (MOCVD)
processes, but because of its instability, it has to be
The ground state electronic configuration of antimony generated on site.1 SbH2 , H2 SbOH, and HSbO2 are products
is [Kr] 4d10 5s2 5p3 . Its covalent radius is 1.4 A and of the photolysis of SbH3 and O3 in an Ar matrix at
its ionic radii are 0.76 and 0.60 A for six-coordinate 12 K.5
Sb(III) and Sb(V) respectively. Both the +3 and the
+5 oxidation states are stable for antimony. Compounds
with a formal oxidation state of +4 such as Sb2 O4 and
SbBr6 2 are diamagnetic, containing equal amounts of 3 ANTIMONIDES
Sb(III) and Sb(V). Negative oxidation states are found in
alkali metal antimonides. The most frequently encountered
coordination numbers are 3 (e.g. trigonal pyramidal in Reduction of antimony by alkali metals or by other
SbH3 ), 4 (tetrahedral in Sb(CH3 )4 + , -trigonal bipyramidal methods leads to alkali metal antimonides (Zintl anions)
in (CH3 )2 SbBr2 ), 5 (square pyramidal in SbF5 2 , SbPh5 , of various types. Known antimonides include isolated
trigonal bipyramidal in SbF5 ), and 6 (octahedral Sb in Sb3 ions (in Li3 Sb, Na3 Sb), dumbbells Sb2 4 in
SbBr6 3 , SbF6 ). Also, coordination numbers 1 (SbSb) and Cs4 Sb2 , discrete antimony chains, for example, Sb6 8
2 (stibabenzene, C6 H5 Sb, RSb=SbR, RSb=CR2 , Ph2 Sb ) are in SrSb3 , infinite spirals (Sb )x (in NaSb, RbSb), pla-
known. nar four-membered rings Sb4 2 in K(crypt)3 Sb4 , Sb7 3
cages in Cs3 Sb7 or Na3 Sb7 3TMEDA3THF (TMEDA =
tetramethylethylenediamine, THF = tetrahydrofuran), and net
shaped anions Sb3 2 in BaSb3 .6,7 Also, transition met-
2 ANTIMONY HYDRIDES als, lanthanides and actinides, form a variety of inter-
metallic compounds with antimony. Typical transition
The most important antimony hydride, stibine, SbH3 is a metal/antimony intermetallics are MSb2 (M = Ni, Pd, Pt,
malodorous, extremely toxic gas (bp 18 C, mp 88 C) Au) with Sb2 units and MSb3 (M = Co, Rh, Ir) with Sb4
formed from soluble antimony compounds and hydrogen in rings.
ANTIMONY: INORGANIC CHEMISTRY 3
4 ANTIMONY GROUP 13 METAL (Al, Ga, In) anions, for example, [Sb(NR)3 ]3 , [Sb2 (NR)2 (-NR)2 ]2 ,
AND GROUP 15 METAL (Si, Ge, Sn, Pb) or [Sb3 (NR2 )2 (-NR)4 ].23 The reaction between SbCl3 and
COMPOUNDS Li[NHPh] affords the remarkable twenty-four-membered
imido antimony metallacycles Sb12 (NPh)18 (2).23,24
Important intermetallics are the III V semiconductors for The reaction of SbCl3 with [(PNR)2 (NRLiTHF)2 ] leads to
infrared detectors AlSb (band gap, 2.2 eV), GaSb (band a polycyclic cage complex of the formula [(PNR)2 (NR)2 Sb]Cl
gap, 0.7 eV), and InSb (band gap, 0.2 eV), which can where antimony is bonded to three nitrogen and one
be used as diodes and Hall effect devices. Precursors of chlorine atom.25 Antimony in a square planar environment
these semiconductors are products obtained by reactions of four nitrogen atoms exists in porphyrins and related
of Sb(SiR3 )3 and alkyl derivatives of group 13 metals, for macrocycles.26,27 SbN bonds also exist in antimony azides.
example, Lewis acid base adducts R3 MSb(SiR3 )3 (M = Al, The mixed chloride diazide SbCl(N3 )2 is formed from NaN3
Ga, In; R = alkyl) or heterocycles [R2 MSb(SiMe3 )2 ]n (n = and SbCl3 at room temperature.28
2, 3).811
Known molecular compounds with bonds between
antimony and group 15 metals (M = Si, Ge, Sn, Pb) include Ph
organometal stibines (R3 M)3 Sb, distibines (R3 M)4 Sb2 , or the Ph Sb N Ph
silyl antimonide [(DME)LiSb(SiMe3 )2 ].9,1216 The reaction N N
of the latter with iPr3 SiCl yields the mixed stibine Ph N Sb Sb
iPr3 SiSb(SiMe3 )2 .9 Sodium tri(tert-butyl)silanide reacts with Ph N
N Sb Ph
SbCl3 to form the bicyclic stibine R6 Sb8 (1) (equation 4).17 Ph N
Sb
Ph
R N Sb
N Ph
Ph N
Sb R Sb N
+24NaSitBu2 Ph
8SbCl3 R Sb Sb Sb Sb
9tBu3Si-SitBu3 Ph
Sb Sb Sb R (4) Ph N
24NaCl
R Sb N Ph Sb N
Sb Sb N
R N Ph
N
R = Si Bu3
t
(1)
Ph N Sb Ph
2
H H
O O Monomeric Sb(III) dialkylcarbamato complexes Sb(O2
C C C C
CNR2 )3 form in reactions between trisamidostibines and CO2
O O O O (equation 6).37
Sb Sb
O O O O
Sb(NR2 )3 + 3CO2 Sb(O2 CNR2 )3 (6)
C C C C
O H H O
tartar emetic 6.2 Antimony Sulfides, Selenides, Tellurides
Cp(CO)2Fe Fe(CO)2Cp
I Sb Fe(CO)3
Scheme 5
complexes of the type (CO)n MSb (n = 6, M = Cr, Mo, 9. C. von Hanisch, P. Scheer, and B. Rolli, Eur. J. Solid State
W; n = 5, M = Fe). These unstable species are obtained Inorg. Chem., 2002, 3268.
by reactions of transition-metal carbonyls with the anion 10. E. E. Foos, R. J. Jouet, R. L. Wells, and P. S. White, J. Org.
Sb2 formed by the laser ablation of elemental antimony.60 Chem., 2000, 598, 182.
[{Cpx (CO)2 Fe}SbCl2 ] (Cpx = 5 -C5 H3 t Bu) reacts with Mg 11. E. E. Foos, R. J. Jouet, R. L. Wells, A. L. Rheingold, and L. M.
to give [Sb{Fe(CO)2 Cpx }3 ] or with Na2 [Fe(CO)4 ] to give Liable-Sands, J. Org. Chem., 1999, 582, 45.
the clusters [{SbFe(CO)2 Cpx }3 {Fe(CO)3 }4 ] and [{Fe3 (CO)9 } 12. C. J. Carmalt and J. W. Steed, Polyhedron, 2000, 19, 1639.
{SbFe(CO)2 Cpx }2 ].61,62
13. C. von Hanisch, Z. Anorg. Allg. Chem., 2000, 627, 1414.
Oxidation of [NEt4 ]2 [Ni15 Sb(CO)24 ] with SbCl3 leads to
the [Ni31 Sb4 (CO)40 ]6 hexa anion, which displays four semi- 14. H. J. Breunig, Thermochromism of organometallic derivatives
interstitial Sb atoms.63 The [Fe2 Sb(CO)5 Cp]4 (Cp = C5 H5 ) containing As, Sb, or Bi, in The Chemistry of Organic Arsenic,
cluster is formed by thermolysis of [Et4 N][{Fe(CO)4 }2 Antimony and Bismuth Compounds, ed. S. Patai, John Wiley
{Fe(CO)2 Cp}SbI] (Scheme 5). The cluster contains the cubane & Sons, Chichester, UK, 1994, p. 441.
[Fe4 Sb4 ] core.64 15. H. J. Breunig and R. Rosler, Coord. Chem. Rev., 1997, 163, 33.
The reaction of SbCl3 with [Ni6 (CO)12 ]2 gives the 16. H. J. Breunig, M. Jonsson, R. Rosler, and E. Lork, J. Org.
cluster anions [Ni15 Sb(CO)24 ]2 and [Ni11 Sb2 (CO)18 ]3 .65 Chem., 2000, 608, 60.
Sb2 , cyclo-Sb3 , and cyclo-Sb5 units are stabilized as ligands 17. M. Westerhausen, S. Weinrich, and P. Mayer, Z. Anorg. Allg.
in transition-metal complexes, for example, the tetrahedranes Chem., 2003, 629, 1153.
Sb2 [Mo(CO)2 Cp ]2 and Sb3 [Mo(CO)2 Cp ], or in the triple- 18. M. Ates, H. J. Breunig, and M. Denker, Phosphorus, Sulfur
decker Cpx Mo(Sb5 )MoCpx .66,67 Silicon, 1995, 102, 287.
19. A. Bashall, M. A. Beswick, N. Feeder, A. D. Hopkins, S. J.
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Antimony: Organometallic scrambling reaction (equation 2) of Me2 SbBr in the absence
of a solvent.6
Chemistry 2Me2 SbBr Me3 Sb + MeSbBr2 (2)
Hans Joachim Breunig Me3 Sb is also formed in very low yield by the process of
University of Bremen, Bremen, Germany biomethylation of Sb2 O3 or other antimony compounds by the
wood rotting fungus Phaeolus schweinitzii.7
Based in part on the article Antimony: Organometallic Chemistry Other useful organometallic reagents for the preparation
by Alan Berry which appeared in the Encyclopedia of Inorganic
Chemistry, First Edition. of tertiary stibines or related heterocyclic compounds are
compounds of lithium, aluminum, tin, copper, zirconium, and
other metals.813 In most cases, these metal compounds are
1 Introduction 1 reacted with antimony chlorides or bromides. Good yields
2 Trivalent Antimony 1 of tertiary stibines were, however, also obtained by the
3 Compounds with Sb Sb Single Bonds 4 interaction (equation 3) of trialkylaluminium reagents and
4 Low-coordination Organoantimony Chemistry 5 tris(dimethylamino)stibine.11
5 Pentavalent Organoantimony Compounds 6
6 Transition Metal Complexes with Organoantimony 6R3 Al + 2Sb(NMe2 )3 2R3 Sb + 3[R2 AlNMe2 ]2 (3)
Ligands 7
7 Further Reading 7
8 References 7 A dilithium reagent is used for the synthesis of a stibaindol (1)
(equation 4).13
SiMe3
+ PhSbCl2
Li SiMe3
Li Sb
1 INTRODUCTION Ph
(4)
CsF
The first organoantimony compound, triethylstibine, was
Sb
reported in 1850. Since then, a wide range of compounds
Ph
with antimony mainly in the +3 and +5 oxidation states
(1)
was studied. In this article, the focus is mainly on
the results published between 1993 and 2003. Several
general overviews of the chemistry of organoantimony Tertiary stibines are volatile liquids or solids. The aryl
compounds were presented in this period in books and annual derivatives are air-stable but the trialkyl stibines are air-
reviews.15 sensitive compounds, with at least the lower members being
spontaneously flammable in air. They are strong reducing
agents and can be used for the removal of halogen atoms from
many substrates.
Triphenylstibine Ph3 Sb and, less frequently, trialkylstibines
2 TRIVALENT ANTIMONY or bi- and tridentate stibine ligands, for example, CH2 (SbPh2 )2
and CH3 C(CH2 SbPh2 )3 are used as donor ligands in transition
metal complexes.14,15 (CF3 )3 Sb is exceptional because it does
2.1 Tertiary Stibines not act as a donor but as an electron pair acceptor in the
reaction with a carbene (equation 5).16
A common method for the synthesis of tertiary stibines with
alkyl, aryl, or other organic groups is the reaction between
Grignard reagents and SbCl3 (equation 1) in diethylether or (CF3 )3 Sb + CN(Mes)C2 (Cl)2 NMes
tetrahydrofuran.
(CF3 )3 SbCN(Mes)C2 (Cl)2 NMes (5)
partial substitution of halogens in antimony trihalides using 2.3 Diorganoantimony Cations and Anions
organometallic reagents.17,18 The latter method was used in
the reaction of tris(trifluoromethyl)phenyl lithium and anti- Diorganoantimony cations R2 Sb+ with six valence
mony trichloride, which yields the corresponding chlorostibine electrons at antimony are unstable species. Coordination
(equation 6).19 of donors leads to stable cationic adducts. One example is
[SbPh2 {OP(NMe2 )3 }2 ]PF6 , where two hexamethylphosphoric
2RLi + SbCl3 R2 SbCl + 2LiCl (6) acid triamide molecules are coordinated to the cationic
R = 2,4,6-(CF3 )3 C6 H2 antimony center.28 Intramolecular coordination of both
amine arms of the aryl ligands leads to the stabilization
A racemic monochloride with a chiral antimony center, of [SbR2 ][PF6 ] (R = 2-Me2 NCH2 C6 H4 ).28 Cationic Sb(III)
RR SbCl [R = 2-(Me2 NCH2 )C6 H4 , R = CH(SiMe3 )2 ], is compounds exist also as sandwich complexes in
formed by the reaction of R SbCl2 with RLi. The [Cp2 Sb][AlCl4 ](Cp = C5 Me5 , C5 H2 t Bu3 -1,2,4).29
compound is stable to inversion up to 160 C in solution.20 Anionic diorganoantimony species, that is, diorganoanti-
Alkylantimony(III)chlorides of high purity are formed by monides R2 Sb are formed by cleavage of tertiary stibines
reacting alkylphenylstibines with gaseous HCl. This method with alkali metals or by metalation of primary stibines. Cleav-
was used for the synthesis of Me2 SbCl from PhSbMe2 . age of a Sb C bond of triarylstibines with formation of
Subsequent halide exchange with NaI gives crystalline diarylantimonides is easily achieved in solutions of sodium in
Me2 SbI.21 liquid ammonia (equation 7).30
Many organoantimony(III) halides are Lewis amphoteric.
R3 Sb + 2Na R2 SbNa + RNa (7)
They have acidic sites on the Sb atoms and they are also
basic through the lone pairs of electrons on the halogen
Metalation of RR SbH with BuLi gives the chiral
atoms. A frequently encountered consequence of this dual
lithium antimonide RR SbLi [R = 2-(Me2 NCH2 C6 H4 , R =
nature is the formation of coordination polymers in the solid
CH(SiMe3 )2 ] (4) that forms RR SbNa after transmetalation
state. The resulting structures formed through self-assembly
with t BuONa in the presence of tetramethylethylenediamine.20
of molecules were considered in a book and in a review
The pendant amine arm of (4) is coordinated to the alkali metal
article.22,23 The Lewis acidity of organoantimony halides is
center.
also reflected in the tendency to form stable adducts with
neutral donors or with halide anions. The 1:1 adduct (2)
is formed by reaction of methylantimony dichloride with
2,2 -bipyridine.24
Me Me N Li Sb
Cl Cl R
Me
Sb thf thf
N N (4)
Intramolecular NSb interactions exist in RSbCl2 [R = 6- The chemistry of organoantimony hydrides (primary
Me-2-Pyr(Me3 Si)2 C].25 The addition of tetramethylstibonium stibines, RSbH2 , or secondary stibines, R2 SbH) has been
iodide to PhSbI2 leads to the salts [Me4 Sb]2 [Ph2 Sb2 I6 ]. The discussed in a recent review article.31 Hydrides with smaller
dianions [Ph2 Sb2 I6 ]2 (3) form as cis- and trans-isomers.26 organic groups tend to be less stable and result in lower
yields, whereas those with bulkier groups are more stable
and yields of 50% and above are common. Comparatively
Ph
2
Ph Ph
2 stable monomeric species of the type RSbH2 and R2 SbH have
I I I I I I been formed with substituents R, which may be either an alkyl
Sb Sb Sb Sb group containing no -hydrogen atoms, for example, Me3CH2 ,
I I I I I I
Ph Me3 SiCH2 (Me3 Si)2 CH, or bulky aryl groups. The primary
stibine 2,6-Trip2 C6 H3 SbH2 (Trip = 2,4,6-triisopropylphenyl)
trans-(3) cis-(3)
is of extraordinary stability. It is a white crystalline solid
that decomposes at 195 C and is indefinitely stable at room
Self-association occurs also in organoantimony pseudo- temperature under N2 in the absence of light.32 The reaction
halide derivatives. K[PhSb(SCN)3 ] has a polymeric structure with BuLi gives 2,6-Trip2 C6 H3 (Li)SbH.
in which the S atoms of one SCN are in bridging positions The most frequently used synthetic procedure for
between pairs of Sb atoms.27 organoantimony hydrides is the reaction of an organoantimony
ANTIMONY: ORGANOMETALLIC CHEMISTRY 3
halide with lithium aluminum hydride at low temperatures in [(R2 Sb)3 E]+ , RSb(ER)2 , and R2 SbER, (E = group 16
an ether solvent. Isobutylstibine Me2 CHCH2 SbH2 is formed in element).
59% yield by this method.33 Not only a primary stibine RSbH2 A four-membered heterocycle trans-(RSbO)2 [R = 2,4,6-
but also a distibine R(H)SbSb(H)R [R = (Me3 Si)2 CH] is (Me3 Si)2 CH)3 C6 H2 ] is formed by reaction of single
formed when bis(trimethylsilyl)methylantimony dichloride is crystals of RSb=SbR with atmospheric oxygen with
reacted with LiAlH4 .34 The distibine is a yellow crystalline retention of crystallinity.45,46 Hydrolysis of RSbCl2 [R =
compound that exists in the meso form in the solid state. A (Me3 Si)2 CH] leads to cyclo-(RSbO)n (n = 3, 4). The core of
racemic chiral stibine RR SbH R = (Me3 Si)2 CH, R = CH3 crystalline cyclo-[(Me3 Si)2 (CHSbO)4 H2 O] is a boat-shaped
is formed from RSbH2 and MeI in the presence of a 8-membered Sb4 O4 ring with the organic substituents in
base.34 trans positions.47 Distibine oxides of the type R2 SbOSbR2
Other methods of organoantimony hydride synthesis are obtained by hydrolysis of diorganoantimony halides or
are reactions of R2 SbLi with (Me3 NH)Cl or methanolysis by oxygenation of distibines. (Me2 Sb)2 O is best prepared
of silylstibines RSb(SiMe3 )2 or R2 SbSiMe3 . Vinyl stibine by reaction of Me2 SbBr with aqueous NaOH. In the solid
H2 C=C(H)-SbH2 is obtained from vinyl tributylstannane on state, the molecules are arranged as zigzag chains through
successive reactions (equation 8) with SbCl3 and Bu3 SnH.35 intermolecular Sb O interactions (Figure 1).48
Oxygen in the environment of three antimony atoms
SbCl3
H2 C=C(H)SnBu3 H2 C=C(H)SbCl2 exists also in the planar oxonium salt [(Me2 Sb)3 O]Br,
which is formed by reaction of (Me2 Sb)2 O with Me2 SbBr.49
Bu3 SnH
H2 C=C(H)SbH2 (8) Tetraaryldistibine oxides are formed by air oxidation of the
corresponding distibines.50
Arylstibines RSbH2 , R = Ph, p-Tol react with a range of The most common method for synthesizing
organic substrates, for example, styrene, alkynes, prochiral organoantimony(III) mono and di alkoxides is the reaction
ketones, with transfer of the hydrogen atoms.36 RSbH2 of R2 SbX or RSbX2 with the appropriate sodium alkoxide.
(R = Me3 SiCH2 ) can be used together with trimethylindium Related organometallic compounds are the group 14 element
to deposit thin films of InSb at 450 C.37 derivatives RSb(OMR3 )2 (M = Si, Ge, Sn; R = alkyl, aryl).51
[R2 GaOSbEt2 ]2 (5), a compound where oxygen is in the
environment of two Ga atoms and a Sb center, is formed by
2.5 Group 1315 Element Derivatives of Sb(III) reaction of R3 Ga (R = Me3 SiCH2 ), Et4 Sb2 , and oxygen.52
Organoantimony compounds with bonds between Sb and
group 13 elements were discussed in a recent review.38 They
are known as Lewis acid base adducts R3 Sb-MR3 (M = Al, SbEt2
Ga, In) and as four- or six-membered heterocycles (R2 Sb- R O R
MR2 )n (n = 2, 4). Pyrolysis of these compounds leads to the Ga Ga
semiconducting materials AlSb, GaSb, and InSb. R O R
Organoantimony group 14 element compounds include
SbEt2
organometallic stibines of the types R2 SbMR3 and RSb(MR3 )2
(M = Si, Ge, Sn). They are formed by reactions of R2 SbLi R = (Me3SiCH2)
with R3 MCl (M = Si, Ge, Sn), by dehalogenation of RSbBr2 (5)
and Me3 MCl with Mg, or by exchange reactions.39,40 The silyl
derivatives R2 SbSiR3 and RSb(SiR3 )2 are useful reagents for
the synthesis of compounds with Sb H, Sb Sb, or Sb metal Organoantimony derivatives of the heavier chalcogens
bonds.41 of the types (RSbE)n (E = S, Se, Te) are formed by
Nitrogen derivatives of organoantimony(III) are known as
moisture-sensitive amides R2 SbNR2 , RSb(NR2 )2 , and stibino
amines (R2 Sb)3 N. The amides are obtained from the reactions Me
of organoantimony(III) mono- and dihalides with LiNR2 or Sb
Me
R2 NH in the presence of Et3 N.42,43 Tris(diphenylstibino)amine Me Me
(Ph2 Sb)3 N is formed by ammonolysis of Ph2 SbCl in liquid O
Sb
NH3 .44 It contains an almost planar Sb3 N core. Sb
Me
O Me
Me Sb
2.6 Chalcogen Derivatives of Sb(III) Me
elimination of salt from RSbCl2 and Na2 E. Reaction of formed by reaction of R2 SbBr with Mg, by elimina-
RSbH2 with sulfur provides the cyclic polysulfides RSbSn tion of dihydrogen from R2 SbH, by reactions of R2 SbNa
(R = 2,4,6-[(Me3 Si)2 CH]3 C6 H2 , n = 5, 7).53 The binuclear with BrCH2 CH2 Br in liquid NH3 , or by other methods.
chalcogenides (R2 Sb)2 E are obtained by insertion of elemental Distibines like almost all organometallic compounds with
chalcogens into the Sb Sb bonds of distibines or by reaction Sb Sb bonds are yellow. However, the distibines R2 Sb-
of R2 SbCl with Na2 E.54,55 Reaction of distibines with SbR2 [R = CH3 , R2 = Me2 C4 H2 ] are exceptional. They form
disulfides, diselenides, or ditellurides give monochalcogentate red solid phases that consist of linear chains of molecules
R2 SbER (E = S, Se, Te), which undergo redistribution to with close intermolecular Sb Sb contacts. Cyclostibines
dichalcogenates and other products like RSb(ER)2 .54,56,57 The with known crystal structures are trimers (tristibiranes)
affinity of antimony to sulfur is reflected in the stability R3 Sb3 [R = (Me3 Si)2 CH], tetramers (tetrastibetanes) R4 Sb4
of organoantimony(III) complexes with bidentate sulfur [R = t Bu, (Me3 Si)2 CH, Me5 C5 ], pentamers (pentastiboles)
ligands, for example, dithiocarbamates and phosphinates.54 R5 Sb5 ([R = Me3 CCH2 ), or hexamers (hexastibanes) R6 Sb6
The dithiophosphinate Me2 SbS2 PMe2 has a polymeric chain (R = Ph, Tol). Cyclo-R3 Sb3 has been prepared by reac-
structure with intermolecular Sb S contacts. It is formed by tion of RSbCl2 with Li3 Sb or by photochemical ring
reaction of Me2 SbSbMe2 with [Me2 P(S)S]2 .58 The reaction contraction of the corresponding tetrastibetane. The rings
of PhSbCl2 with K[(SPPh2 )2 N] gives PhSb[(SPPh2 )2 N]2 (6), cyclo-Rn Sbn (n = 4 6) are formed from RSbBr2 and Mg
a complex where the Sb center is in a square pyramidal
in THF, by air oxidation of RSb(SiMe3 )2 , or by elim-
environment.59
ination of hydrogen from RSbH2 . Several catena-stibines
R2 Sb(SbR)n SbR2 exist as components of ring-chain equilibria
Ph Ph
(equation 9).
Ph Ph
Ph
P S S P
N Sb N R2Sb-SbR-SbR2 1/n cyclo-(RSb)n + R4Sb2
P S S P
Ph R
Ph Ph R
Ph
R Sb
(6) Cr(CO)4(nbd) Sb
Cr(CO)4 (9)
Sb
R Sb
1,3-dioxa, -thia-, -selena-, tellura-ferrocenophanes (7) R
R
containing antimony in the central bridge position are formed
by HCl elimination from t BuSbCl2 and the corresponding R = Me3SiCH2, R= Me, Ph; nbd = norbornadiene
ferrocene derivatives containing EH or ELi bonds.60
E = O, S, Se, Te
(7) R
R Sb Sb
Mg Sb SbCl3, pyridine
RSbH2
RSbCl2 Sb Sb
Sb R
Sb Sb
3 COMPOUNDS WITH SbSb SINGLE BONDS
R
hn R = (Me3Si)2CH
Known neutral organometallic compounds with nor-
mal covalent Sb Sb bonds comprise distibines, R2 SbSbR2 , R
cyclostibines Rn Sbn (n = 3 6), catena-stibines R2 Sb(Sb- Sb Sb
R)n SbR2 (n = 1,2), and polycycles Rn Sbm (m > n). Dative Sb R
Sb Sb bonds exist in the adducts R3 Sb-Sb(R)X2 , or in
R
ionic species of the types R3 Sb-SbR2 + or [R2 Sb-SbR2 -
SbR2 ]+ . Also dicationic and anionic species, [R3 Sb-SbR3 ]2+
and [R2 Sb-Sb-SbR2 ] , are known.54,6163 Distibines are Scheme 1
ANTIMONY: ORGANOMETALLIC CHEMISTRY 5
A pentachloro hexastibane Sb6 R5 Cl is obtained by reaction with 1,3-butadienes.68 Stibaalkene monomers have been con-
of RSbCl2 with Na/K (equation 10).65 sidered as intermediates in various reactions. Structurally
authenticated compounds with Sb=C bonds are stiba dion-
R ato complexes, stiba enols, or distibabutadienes formed from
R
LiSb(SiMe3 )2 and RCOCl. (Scheme 2).45,69,70
Sb
Sb Cl Monomeric distibenes trans-RSb=SbR exist with pro-
Na, K
RSbCl2 R Sb Sb Sb (10) tection of very bulky aryl groups. They are formed by
Sb R dehalogenation of the corresponding dihalides with Mg or
by deselenation of a triselenatristibane (Scheme 3).45,46,71,72
R
With sterical protection also, a compound of the type
RBi = SbR featuring a double bond between antimony and
t
Bu4 Sb4 is a source for the syntheses of complexes with bismuth is stabilized.72
Sbn ligands or four polynuclear antimonides.63 Reduction of Known structures where two coordinate Sb centers are
t
Bu4 Sb4 with alkali metals (M = Li, Na, K) in the presence incorporated in aromatic ring systems are shown in Figure 2.
of (Me2 NCH2 CH2 )2 NMe gives the anionic species t Bu4 Sb3 The chemistry of these heterocycles is well documented in
and t Bu3 Sb2 (equation 11).61,63 review articles.45,73
R R
M R Sb R M
cyclo-(RSb)n R R Sb Sb (11)
R
Sb Sb
R Me3SiO C SiMe3
R = t Bu, M = alkali metal RCOCl
(Me3Si)2SbLi Sb Sb
Me3Si C OSiMe3
Cationic species with Sb Sb bonds are formed by
RCOCl R
scrambling reactions or addition of a stibine donor to a Lewis
acidic antimony center. Scrambling reactions of Me2 SbBr lead R = Mes, Mes*
to the ionic complex (Me3 Sb-SbMe2 )2 (MeSbBr2 )2 containing
R Sb R R Sb R
cations (8) that consist of pyramidal Me3 Sb bonded to bent
HCl
Me2 Sb units through short (2.82 A) Sb Sb bonds.66 R=
= Mes*
O O O O
Li H
RSbCl2 Sb Sb (RSbSe)3
R
R= 2,6-Mes2C6H3, 2,6-(iPr3C6H2)2C6H3 R = 2,4,6-(Me3Si2)2CH)3C6H2
Scheme 3
5 PENTAVALENT ORGANOANTIMONY a 1:1 adduct between Ph2 SbCl3 and Ph3 SbO.79 Organoanti-
COMPOUNDS mony tetrahalides are the least stable in this series. However,
adducts with donor ligands or the type RSbX4 L are known.
Antimony forms numerous stable pentavalent organo-
metallic compounds; among these are penta alkyls and aryls, 5.3 Organoantimony(V) Chalcogen and Nitrogen
mixed organohalides, and various chalcogen and nitrogen Derivatives
derivatives.
A series of compounds analogous to organoantimony
halides exist also for alkoxides and other compounds of
5.1 Penta Alkyls and Aryls the type Rn Sb(OR )(5n ). Antimony tetraorganyls R4 SbOR
are formed from R5 Sb and ROH or from R4 SbCl and
The pentaorgano compounds are thermally stable but air MOR (M = Na, Ag).80 Reactions of R5 Sb with water give
sensitive. They are generally synthesized by the reaction of tetraorganoantimony hydroxides R4 SbOH.
Grignard or organolithium reagents with triorganoantimony Compounds of the type R3 Sb(OR )2 are usually obtained
dihalides and have monomeric molecular structures. Me5 Sb by reactions of R3 SbX2 with NaOR . They adopt trigonal
and Ph3 Me2 Sb are trigonal bipyramidal molecules.74 Ph5 Sb is, bipyramidal structures with the oxygen atoms in axial
however, approximately square pyramidal in the solid state.75 positions. Hydrolysis of R3 SbX2 can lead to dihydroxides
The lithium salt of the octahedral [Me6 Sb] ion is obtained R3 Sb(OH)2 , hydroxy halides R3 Sb(X)OH, or binuclear
from Me5 Sb and MeLi in tetrahydrofuran.75 Reactions of condensation products (R3 SbX)2 O.8183 Heating R3 Sb(OH)2
R5 Sb with protic species including acids, alcohols, and thiols under vacuum gives R3 SbO. A complex with intramolecular
give R4 SbX products. coordination of two oxygen atoms to an R3 Sb unit is the
complex (10) that contains chiral centers at antimony and
at two carbon atoms. It exists as a pair of configurationally
5.2 Organoantimony(V) Halides and Stibonium Salts stable diastereomers. The rates of interconversion between the
diastereomers is accelerated in donor solvents and probably
Examples of organoantimony(V) halides exist, ranging procedes through a hexacoordinate transition state.84
from RSbX4 to R4 SbX. The stability decreases according to
R4 SbX, R3 SbX2 , >R2 SbX3 >RSbX4 . Tetraorganoantimon-
halides R4 SbX form by addition of RX to R3 Sb.76 They usually
have ionic structures of stibonium salts, R4 Sb+ X . Ph4 SbI, CH3
however, is a molecular species with distorted trigonal bipyra- CF3
midal geometry.77 Triorganoantimony dihalides are formed Sb O
by addition of X2 to the corresponding to triorganostibines. R
They adopt trigonal bipyramidal structures with axial halogen O
atoms.78 The reductive elimination of RX from R3 SbX2 is H3C CF3
an important synthetic pathway leading to diorganoantimony
R = p-Tol
halides. Diorganoantimony trihalides are generally less stable
(10)
than their dihalide counterparts undergoing reductive elim-
ination to RX and RSbX2 easily. They usually are strong
Lewis acids and tend to form dimers with bridging halogen Alkoxides of the type R2 Sb(OR)3 react with water with
atoms in the solid state unless protected by bulky groups. the formation of stibinic acids R2 Sb(O)OH. Their anhydrides
One example for a dimeric structure is Me2 SbCl3 , where the have the formula (R2 Sb)4 O6 . They are molecular compounds
methyl groups are on both sides of the Cl2 Sb(-Cl)2 SbCl2 with bridging oxygen atoms between four Sb atoms in a
plane and the environment of the Sb centers is octahedral. cage structure (11). The anhydrides (11) are formed by air
The Lewis acidic character is exemplified by the formation of oxidation of distibines R2 Sb-SbR2 or by other methods.
ANTIMONY: ORGANOMETALLIC CHEMISTRY 7
R R
R Sb O R R
Sb R O
R Sb Sb R
O2 O H2O2 O
R2Sb-O-SbR2 O O
O O O O O
Sb O
R Sb Sb R
R = Ph, Tol O
Sb R R
R O
R R R
(11) (12)
Scheme 4
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Arsenic: Inorganic issues. Arsenic acid, AsO(OH)3 , is still used in the formulation
of wood preservatives but banned recently in the United States.
Chemistry Sodium arsenate is used to control fungi which cause measles
on grapes. Sodium arsenite and monomethylarsonate are used
as simple bulk weedkillers, and arsenicals such as sodium
Miguel-Angel Munoz-Hernandez arsenate and copper acetoarsenite [Cu(CH3 COO)2 Cu(AsO2 )2 ]
Universidad Autonoma del Estado de Morelos, Centro de Investi- can be found in commercial household insecticides. Arsenic
gaciones Qumicas, Morelos, Mexico is also a common component of fire retardants.1
The toxicity of arsenic has been put into practical use in
Based in part on the article Arsenic: Inorganic Chemistry by Ralph A. medicine. Ehrlich in 1909 developed Salvarsan, the trade
Zingaro which appeared in the Encyclopedia of Inorganic Chemistry, name for arsphenamine (1), which was the first modern
First Edition.
chemotherapeutic agent effective in the treatment of syphilis,
which was eventually phased out by better organoarsenicals
1 Introduction 1 and latter by penicillin. Some specialist arsenical drugs are
2 Preparation 2 still the treatment of choice for amoebic infections like
3 Intermetallic and Zintl Phases with Arsenic 2 glycobiarsol (2).2
4 Arsenic Hydrides 3
5 Arsenic Halides 5
HCl H2N NH2 HCl
6 Arsenic Chalcogen Compounds 7
7 Arsenic Compounds Containing Carbon 15
8 Arsenic Pnictogen Compounds and Complexes HO As As OH
Based on Ligands with Pnictogen Donor Atoms 15
9 Arsenic in the Environment 18 (1)
10 Related Articles 20
11 References 20
O
HOCH2 C NH As OBi O
O OH
Abbreviations
(2)
Ka = Acidity constant; cm = Centimeter; en = Ethylendi-
amine; LD50 = 50% of a lethal dose; Et = Arsenic has a prominent place in the development of
ethyl; i-Bu = Isobutyl; hcp = Hexagonal close packed; modern inorganic chemistry. Lois-Claude Cadet de Gassicourt
i-Pr = Isopropyl; LED = Light-emitting diode; Me = in 1757 during his experiments with arsenic-containing cobalt
Methyl; MOCVD = Metalorganic chemical vapor depo- ores, CoAs2 and CoAsS2 , prepared by the combination of
sition; E = Normal standard potential; NMR = Nuclear arsenious oxide, As2 O3 , and potassium acetate, CH3 CO2 K,
magnetic resonance; n-Bu = n-butyl; n-Pr = n-propyl; a red malodorous fuming liquid (Cadets fuming liquid)
OEP = Octaethylporphyrin; t-Bu = Tert-butyl; THF = that contained the first organometallic or more rigorously
Tetrahydrofurane; TPP = Tetraphenylporphyrin; V = Volt. stated organometallioid compounds (equation 1). Latter, in
the early nineteenth century it was found that the main
components of the red liquid are tetramethyldiarsine (3) (40%)
and tetramethyldiarsine oxide (4) (56%).3
Me Me Me Me
1 INTRODUCTION As2O3 + 4CH3COOK As As + As O As
Me Me Me Me
(3) (4)
Despite the popular association of arsenic to poisons, the
element has found several uses. Alloys are made with Pb and (1)
to a lesser extent with Cu. The addition of small quantities
of As improves the properties of Pb/Sb for storage batteries. This article will focus on the inorganic chemistry of
Automotive body solder is Pb (92%), Sb (5.0%), Sn (2.5%), arsenic rather on the species that feature arsenic carbon
and As (0.5%). The III-V semiconductors especially GaAs bonds, in which the carbon atom is part of an alkyl or
and InAs are very important in the fabrication of LEDs, aryl group, for example, (3) or (4) (these organoarsenicals
tunnel diodes, infrared emitters, laser windows, and Hall-effect may be found in the article see Arsenic: Organoarsenic
devices. It also found use in agriculture as herbicide and pest Chemistry). Only a few organoarsenicals are presented to
controls but now is very restricted because of environmental illustrate applications or important species that were stabilized
2 ARSENIC: INORGANIC CHEMISTRY
by means of bulky organic ligands such as the arsines (9) (equation 2).
and (10) in Section 4.1.
650 700 C
FeAsS FeS + As(g) As(s) (2)
contains only the latter dimers.8 4As(OH)4 + 3BH4 + 7H+ 3H3 BO3 + 7H2 O + 4AsH3 (4)
4 ARSENIC: INORGANIC CHEMISTRY
AsCl3 + 4SnCl2 + 2HCl As2 H2 + 4SnCl4 (6) examples of these arsines: [(Me3 Si)2 N]2 AsH (9)16 and the air-
stable TripAsH2 (10).18 Interestingly, compound (9) shows a
monomeric pyramidal structure in the solid state contrary to
Tetraarsine dihydride, As4 H2 , prepared from AsH3 and the phosphine analog {[(Me3 Si)2 N]2 PH2 }2 which is planar and
SnCl4 has been characterized as a brown-red amorphous features a planar P2 H2 core.16 The monomeric nature of (9)
solid. It is stable when stored in a dry atmosphere free from has been ascribed to the poor overlap of orbitals between
oxidizing agents. In the absence of air it thermally decomposes As and the H atoms that prevents the formation of H-As-
into arsenic metal and AsH3 . H bridges.
Stable monomeric arsenic hydride species of the type
RAsH2 and R2 AsH have been prepared using substituents
R which have no -hydrogen atoms and are sterically 4.2 Arsine as a Ligand
demanding like (Me3 Si)2 N-,16 trisalkylphenyl ligands (6), 2,6-
bis(trialkylphenyl)phenyl ligands (7)17 and recently triptycene Structurally characterized complexes with AsH3 as a
(Trip) (8).18 Figure 2 shows the X-ray structures of two terminal ligand have yet to be reported.13 This has been
C(11)
C(8)
C(9)
C(10) S(14)
S(13)
C(12)
N(2)
C(7)
As H
C(3)
C(5)
S(1) N(1) C(6)
C(1) S(2)
As1
C(2)
C(4)
(9) (10)
Figure 2 X-ray structures of [(Me3 Si)2 N]2 AsH (9)16 and TripAsH2 (10)18
ARSENIC: INORGANIC CHEMISTRY 5
5 ARSENIC HALIDES
Si AsH2
5.1 Trihalides
AsH2
All the arsenic trihalides are known compounds; this is also
true for the rest of the group 15 cognates. Selected physical
and molecular parameters for the arsenic halides are given in
(11)
Table 2.23
The four arsenic halides are molecular compounds in the
gas phase which have been shown by electron diffraction and
attributed to the weakness of the AsH bond which microwave spectroscopy to have C3v pyramidal structures.23,24
readily promotes elimination of H2 to give AsAs bonded AsF3 must be prepared in anhydrous conditions to prevent
compounds.19 However complexes have been isolated that its hydrolysis from a CaF2 /concentrated H2 SO4 mixture.
contain the AsH2 moiety as in the silane ((i-Pr)3 C6 H2 )(t- The H2 O formed during the course of the reaction can be
Bu)Si(AsH2 )2 (11)20 and the iridiumIII complex trans- effectively sequestered by the sulfuric acid (equation 9).23
[Ir(CO)XH(PEt3 )2 (AsH2 )] with X = Cl, Br (12) prepared In common with other pyramidal molecules AsF3 undergoes
by oxidative addition of AsH3 to the IrI precursor inversion around the arsenic atom. Contrary to other pyramidal
(equation 7).21 Reaction of AsH3 with group 13 compounds molecules that invert trough vertex inversion via a planar
afford oligomeric adduct complexes of the type [R3 M- intermediate (D3h ), AsF3 has been shown by theoretical
AsH3 ]n which on heating eliminate alkanes. This is calculations to invert trough edge inversion via a T-
exemplified by the reaction of t-Bu3 Ga with AsH3 shaped intermediate (C2v ) (Figure 3).25 Although AsF3 is
which renders the trimer [t-Bu2 GaAsH2 ]3 (13) shown in a weaker fluorinating agent than SbF3 , it is preferred for the
equation (8).22 Complex (13) was prepared in the context preparation of high boiling point fluorides despite its obvious
of the search of single-source precursors to GaAs by toxicity since AsCl3 (b.p. 130 C) can be distilled off, for
MOCVD (see Metallic Materials Deposition: Metal-organic example, equation (10).1 AsF3 with chlorine undergoes an
Precursors). interesting oxidation reduction reaction to form [AsCl4 ]+
[AsF6 ] .
AsH2
PEt3 X As4 O6 + 12HF 4AsF3 + 6H2 O (9)
[Ir(CO)X(PEt3)2] + AsH 3 Ir +
[PCl4 ] [PCl6 ] + 2AsF3 +
[PCl4 ] [PF6 ] + 2AsCl3 (10)
H PEt3 (7)
X = Cl, Br CO
(12)
Ga(t-Bu)2 F
F F
H2As AsH2 As F As F As
t-Bu3Ga + AsH 3 [t-Bu3Ga-AsH3] F F
(t-Bu)2Ga Ga(t-Bu)2 F F
AsH2
(13)
Figure 3 Inversion of AsF3 trough edge inversion via a T-shaped
(8) intermediate
Table 2 Selected physical and molecular parameters for the arsenic halides23
The preparation of AsCl3 at laboratory scale has been instability of the heavier arsenic halides can be ascribed to
described in Section 2 (see equation 3). By comparison to a tendency towards reduction to give the arsenic trihalides
the other elements of group 15, the arsenic chlorine bond and elemental halogen (equation 14) owing to the shielding
is more resistant to hydrolysis, therefore its preparation from properties of the underlying full 3d orbitals of arsenic that
aqueous solutions is possible, for example, using concentrated reduce the availability of the electrons in the 4s orbital.23
HCl (equation 11). Other methods for the synthesis of AsCl3
AsX5 AsX3 + X2 (14)
include the direct reaction between the elements, the reac-
tion between As2 O3 and S2 Cl2 , and the treatment of AsF3 X = Cl, Br, I
with PCl3 , PCl5 , PSCl3 , SiCl4 , or SOCl2 . AsBr3 has been
prepared by the direct combination of arsenic metal powder A simple route to prepare AsF5 , which is a colorless gas,
with bromine. The direct reaction between As2 O3 , sulfur and involves the reaction of fluorine with arsenic. In the laboratory
bromine has also been described (equation 12). The synthesis it is conveniently prepared by the reaction between AsF3 ,
of AsI3 an orange-red crystalline solid can be accomplished in SbF5 , and bromine (equation 15). The electron diffraction
aqueous solution by the reaction between potassium iodide and structure in the gas phase of AsF5 shows the expected trigonal
arsenic trioxide in concentrated HCl (equation 13). The solid- bipyramidal arrangement around arsenic with axial bond
state structure of AsCl3 shows three short molecular AsCl lengths of 1.711 A and equatorial bond lengths of 1.656 A.
bonds (Table 2) and three longer intermolecular bonds from 2SbF5 + Br2 + AsF3 AsF5 + 2SbBrF4 (15)
the nearest chloride atoms from other AsCl3 molecule afford-
ing AsCl6 with a distorted octahedral geometry. The same Arsenic pentachloride was an elusive compound until it was
structure is found for AsBr3 and AsI3 .23 AsCl3 is not as suscep- finally obtained by the ultraviolet irradiation of an AsCl3 /Cl2
tible to nucleophilic attack as PCl3 is. Therefore, the reactions mixture at 105 C. Above 50 C, a redox reaction occurs
of AsCl3 proceed stepwise and it is much easier to stop at a affording AsCl3 and molecular chlorine (see equation 14
lower level of substitution than with PCl3 . A few examples above). The identity of AsCl5 was confirmed by elemental
of reactions that illustrate the reactivity of AsCl3 and the rest analysis and by comparison of its Raman spectrum with those
of arsenic trihalides are given in Scheme 1. Although the self of liquid PCl5 and SbCl5 .26
ionization equilibrium of AsCl3 to give AsCl2 + and AsCl4 is Although not as convenient as PF5 or SbF5 , AsF5 has found
very low (conductivity 1.4 106 ( cm)1 ), AsCl3 has been some use as halide acceptor when a large anion is needed.
used as a nonaqueous solvent for chloride transfer reactions.
As2 O3 + 6HCl 2AsCl3 + 3H2 O (11)
5.3 Mixed Arsenic Halides
2As2 O3 + 3S + 6Br2 4AsBr3 + 3SO2 (12)
As2 O3 + HCl AsCl3 + Kl AsI3 (13)
The mixed arsenic trihalides AsXn X3n and pentahalides
AsXn X5 3n are essentially unstable compounds. But it has
been observed that mixtures of AsCl3 and AsI3 favor the
formation of AsCl2 I according to equation (16). A mixture of
5.2 Pentahalides AsF3 and AlCl3 has been shown to form small amounts of
The only known arsenic pentahalides are AsF5 and AsCl5 AsF2 Cl and AsFCl2 by 19 F NMR. In a similar fashion, the
of which the fluoride is the most stable species. The relative combination of AsCl3 and AsBr3 forms AsCl2 Br and AsBr2 Cl.
2AsCl3 + AsI3
3AsICl2 (16)
(Me2N)3As
AsI3 As(OR)3 All the series of AsF5n Cln (n = 0 5) compounds have all
been observed, although some of them in an argon matrix. The
Me2NH
structure of these halides is as it would be anticipated trigonal
KI ROH bipyramidal with the fluorine atoms in apical positions and
the less electronegative chlorine atoms in equatorial sites.23
AsF3 AsCl3 As2O3
SiF4 H2O
HF/78 C
Scheme 1 AsCH3 + HF + 2AsF3 [(CH3 )3 AsH]+ [As2 F11 ] (17)
ARSENIC: INORGANIC CHEMISTRY 7
A number of chloroarsenate ions are known, and salts It has also been noted that amorphous arsenic reacts with
with the protonated cations of the bases dimethylamine, oxygen at a slower rate than the three recognized crystalline
ethylamine, pyridine, guanidine, and quinoline with the allotropes. Reacting As4 O6 with water affords solutions of
following anions have been prepared: [AsCl4 ] , [AsCl5 ]2 , arsenious acid, which is believed to be As(OH)3 . Arsenite
[AsCl6 ] , [As2 Cl9 ]3 , and [As3 Cl11 ]2 . Other identified ions are formed treating As4 O6 with bases. These ions are
haloarsenates are: [As3 Br12 ]3 , [As6 Br8 ]2 , [As6 I8 ]2 , and formed by ionization of As(OH)3 , namely [AsO(OH)2 ] ,
[As8 I28 ]4 .2830 [AsO2 OH]2 , and [AsO3 ]3 . The mixed-valence ArsenicIII,V
oxide or more commonly known as arsenic dioxide, AsO2 is
formed by heating As4 O6 in an autoclave for fourteen days at
260 C under dioxygen pressure (5 50 MPa).31 The structure
6 ARSENIC CHALCOGEN COMPOUNDS consists of infinite layers of arsenic atoms coordinated to
three or four oxygen atoms. The three coordinated arsenic
atom is considered AsIII and the four coordinated AsV .
6.1 Oxides of Arsenic The complete range of possible oxides between AsIII 4 O6
and AsV4 O10 has been observed by means of matrix-isolation
ArsenicIII oxide, As4 O6 , commonly referred to arsenic techniques. The structures proposed of these oxides are shown
trioxide (As2 O3 ) is the most important arsenic compound in Figure 4.
of commercial value since it is the raw material most ArsenicV oxide, As4 O10 , cannot be formed by the direct
widely used for the synthesis of arsenic compounds. As4 O6 combination between the elements owing to the greater
exists in both molecular and polymeric modifications. The thermodynamic stability of As4 O6 , which promotes the back
cubic modification (arsenolite) contains discrete As4 O6 (14) dissociation reaction illustrated in equation (20). The most
molecules with Td symmetry in an adamantine-like structure useful preparative method involves the oxidation of elemental
in the vapor, liquid and solid phases. The structure is extremely arsenic with concentrated nitric acid, followed by careful
stable and it is the main product obtained by burning arsenic in dehydration of H3 AsO4 (equation 21).
air. The second form of As4 O6 has a monoclinic crystal system
and it is commonly referred as claudetite which exists in two
As4 O6 + 2O2
As4 O10 (20)
forms, claudetite I and II, each of which has a layered structure
of arsenic atoms joined through oxygen atoms. This form of 4H3 AsO4 6H2 O + As4 O10 (21)
As4 O6 is 8.7% more dense than the cubic form. ArsenicIII
oxide is produced as a by-product of the nonferrous metals Hypochlorous, chloric, and perchloric acids also oxidize
industry, primarily from the smelting of copper ores. Naturally the metal or As2 O3 to the pentavalent state. Interestingly,
occurring metal arsenides, realgar, and orpiment also convert dilute HIO3 oxidizes elemental arsenic to the pentavalent state
to the trivalent oxide when roasted in air. The formation of more easily than the concentrated acid.
the trioxide by the roasting of a sulfidic ore is illustrated in
equation (18).23,24
O O
2FeAsS + 5O2 Fe2 O3 + As2 O3 + 2SO2 (18) As As
O O O
O
O As O As
As As O As O O
O O As O As O
O O
O As
As O As3IIIAsVO7 As2IIIAs2VO8
As O C2v
C3v
O
(14) O O
As As
Elemental arsenic undergoes reaction with oxygen to yield O O O O
the trioxide (equation 19). O As O As
As O O As O O
O As O O As O
4As + 3O2 2As2 O3 (19) O O
O
As2IIIAs3VO9 As4VO10
This direct reaction between the elements yields the trioxide C3v Td
almost exclusively. The reaction in air proceeds very slowly,
but the rate increases rapidly with increasing temperature,
decreasing particle size, and in the presence of moisture. Figure 4 Mixed-valence arsenic oxides
8 ARSENIC: INORGANIC CHEMISTRY
6.2 Sulfides of Arsenic As4 S4 is normally prepared as an impure material and must
be purified by sublimation under an atmosphere of CO2 .
Yellow arsenicIII sulfide (orpiment), As2 S3 is prepared As a result of crystal packing, synthetic As4 S4 exists as an
by heating the elements in stoichiometric amounts or by and a forms (16). The As4 S4 units in the solid and in the
heating As4 O6 with sulfur. It is also formed by passing H2 S vapor phases are identical. The form is stable at ambient
into acidified aqueous solutions containing AsIII compounds. temperature and is the same to the mineral realgar, whereas the
Electron diffraction in the gas phase reveals a cage structure form is a high-temperature modification. In the third isomer
As4 S6 similar to As4 O6 . In the solid state, the structure is of realgar -As4 S4 (17) there is arsenic with a coordination
composed of trigonal pyramidal AsS3 units,32 which is quite sphere composed of three, two, and one sulfur neighbors.33
similar to what it is observed for As2 O3 . One of the principal
impurities which accompanies the formation of As2 S3 is
elemental sulfur. This has been removed by extraction with S S As
carbon disulfide. As S
S
As2 S3 has found use in the manufacture of glass, especially As As S
infrared transmitting glass, in pyrotechnics and, because it is S
As As As
a semiconductor, in photoconducting devices. S S As
Arsenic has a very well-developed mixed-valence chem-
a and b-As4S4 g-As4S4
istry with sulfur in part to the occurrence of several of these
species as arsenic minerals. Tetraarsenic trisulfide, As4 S3 , is (16) (17)
orange-yellow and occurs as the mineral dimorphite which is
found in and forms. The solid-state structure of both the
and forms exhibit C3v symmetry (15), differences arise due Pentavalent arsenic sulfides are not well defined. The only
to crystal packing effects.23 accepted compound is As2 S5 which is prepared from H2 S and
a solution of an AsV compound (equation 24) or acidification
of a thioarsenate salt (equation 25).34
As
S H+
S
S 2H3 AsO4 + 5H2 S As2 S5 + 8H2 O (24)
2Na3 AsS4 + 6HCl As2 S5 + 6NaCl 3H2 S (25)
As As
As
(15) 6.3 Selenides of Arsenic
Se
As
Se
(23)
Se(3)
As(1) Se(2)
Se(1)
(24)
As4
As3
As1
As2
(25)
Figure 6 1-D chain-like polymers formed with mononuclear AsE3 building units in Na[AsSe2 ] (23) and K[AsSe3 ]H2 O (24) or with cyclic
molecular building units in (Me4 N)2 As4 S7 (25)37
ARSENIC: INORGANIC CHEMISTRY 11
arrange in the crystal with discrete molecules. To this cations function as templates for the construction of
class of solid-state materials belong also those arsenic this material.
anions that show a cyclic molecular structure with one, Selenium and tellurium arsenates in low oxidation states
two and three arsenic atoms in the ring. Examples are with direct AsAs bonds can be generated either by controlled
those anions found in (Et4 N)[AsSe8 ] (19), Ba2 [As2 Se5 ] (20) oxidation of elemental As or by reduction of a suitable
(anion with a trans configuration), (Ph4 P)2 [As2 S6 ] (21) and binary AsIII chalcogenide, for example, As2Te3 . Rich tellurium
[Sr(en)4 ]2 [As3 Se6 ]Cl (22) which are depicted in Figure 5. phases Na4 [As2 Te4 ] and K4 [As2 Te4 ] are afforded by the first
From (19 22) it is evident that stabilization of these species approach. The dinuclear anion [As2 Te4 ]4 have a gauche (27)
is accomplished with a large cation. conformation in its Na+ salt but a trans (28) conformation in its
Polymer chain-like anions with 1-D dimensionality are K+ or Rb+ salt (Figure 8). The trans conformation generates
formed either by assembling mononuclear AsE3 building a larger cavity that can readily accommodate the voluminous
units like those in Na[AsSe2 ] (23) and K[AsSe3 ]H2 O (24) or cations K+ or Rb+ . A derivative of the trans anion (28) is found
with cyclic molecular building units in (Me4 N)2 [As4 S7 ] (25) in Cs4 [As2 Te6 ] (29), which is the product of the solvothermal
(Figure 6). reaction of Cs2 CO3 and As2 Te3 in methanol at 145 C. The
A 2-D anionic structure has been achieved with substitution of a terminal Te2 by a Te2 2 dumbbell on each
the assembling of individual As4 S4 rings that are con- of the As atoms may be ascribed to the larger Cs+ cation
nected to three further eight-membered rings trough As- (Figure 8). The dinuclear anion [As2 Se5 ]4 (30) present in the
S-As bridges in Cs2 [As8 S13 ] (26) (Figure 7). The Cs+ phase K5 [Ag2 As3 Se9 ] shows direct AsAs bonding between a
As(1)
As(8)
As(2)
As(7)
As(5) As(4)
As(3)
As(6)
(26)
4
Te
Te
Te As
As
As
As Te
Te
Te
(31)
2
Te Te Te Te
Te Te Te Te Te
As As As As
Te Te
Te Te
As As As As
Te Te Te Te Te Te
Te Te Te
(32)
Figure 9 Olygomeric [As4 Te6 ]4 anion (31) in [Ba(en)4 ]2 [As4 Te6 ] or (Me4 N)4 [As4 Te6 ]2en and the polymeric anionic chain [As2Te5 ]2 (32)
in (Me4 N)2 [As2 Te5 ]37
Se1
Se1 Se6
Se2 Se6
Se4
As4
As3
Se3 As2
Se5 Se3
Se2
Figure 10 Boat boat conformation of [As4Se6 ]2 anion (33) in [PPh4 ]2 [As4 Se6 ] and the boat chair conformation (34) in [K(2,2,2-cryptand)]
[As4 Se6 ]38,39
ARSENIC: INORGANIC CHEMISTRY 13
E 2 Te 3
As As
As As As As
As E As
As As As As
As As As As As As
E As As As
(35) (36)
+ Te
As + 3E
3
As
As As
As
As As
As As As
E = Se, Te As As
Figure 11 Arsenic-rich chalcogenide anions related to As11 3 . [As10 E3 ]2 ions (35) found in [PPh4 ]2 [As10 Se3 ], [PPh4 ]2 [As10 Te3 ], and
[K(2,2,2-cryptand)]2 [As10 S3 ]; and the chalcogen-poorest arsenic anion [As11 Te]3 (36) in [K(2,2,2-cryptand)]3 [As11 Te]en37
elemental K in NH3 or ethylenediamine in the presence geometry with the anionic arsenic-containing fragment having
of [PPh4 ]+ or [K(2,2,2-cryptand)]+ as the counterion. The D3 symmetry (equation 29).42
general structure of these anions which are closely related
to that of As11 3 (see also Figure 1) is represented by (35)
in Figure 11. The arsenic chalcogen-poorest known anion,
[As11 Te]3 (36) in [K(2,2,2-cryptand)]3 [As11 Te]en has been W(CO)6 O
obtained by ethylenediamine extraction of a nominal alloy [PPh4][As2Cl8]
THF X X
K8 As8 Te5 in the presence of the sequestering agent 2,2,2- [PPh4]+ As (28)
crypt. The AsAs bond distances in the above mentioned Cr(CO)6 X X
As-rich clusters range from 2.388 to 2.479 A and are [PPh4][AsSBr5]
THF O
significantly shorter than the distances found in elemental
gray arsenic (2.517 A).
X = Cl (38), Br (39)
OH
6.8 Arsenic Complexes Based on Ligands with 2,4-dioxane
AsCl3 + 3 [H7O3]+
Chalcogen Donor Atoms
OH
Inorganic arsenic complexes based on oxygen ligands is
scarce. Simple esters of arsenic acid, As(O)(OR)3 (R = Me,
O
Et, n-Pr, n-Bu, C6 H13 ) have tetragonal structures.2 Reaction
O O (29)
of the diol ligand 2,4-dimethyl-2,4-pentanediol with AsCl3
As
affords an arsenic chloride complex in which the As atom is
part of a six-membered ring (37).40 O O
Reaction of W(CO)6 and [PPh4 ]2 [As2 Cl8 ] and of Cr(CO)6 O
and [PPh4 ][As2 SBr5 ] in THF yields the arsenicV anionic com-
plexes [PPh4 ][AsCl4 (thf )2 ] (38) and [PPh4 ][AsBr4 (thf )2 ] (39) (40)
both complexes display an octahedral coordination with a trans
configuration (equation 28).41 The anionic arsenicV chate- The chemistry of inorganic arsenic complexes with ligands
cholate complex [H7 O3 ][As(C6 H4 O2 )3 ]2,4-dioxane (40) pre- that bear S donor atoms or S and O is more extensive. The
pared from C6 H4 (OH)2 and AsCl3 exhibits an octahedral chemistry of arsenic with xanthate (41), dithiocarbamate (42)
and phosphorus based ligands (43) (Figure 12) has been
reviewed.4346
Homoleptic trisquelate arsenic complexes have been
O O only structurally characterized with ligands (41) and (42).
As
The complexes show mainly a distorted octahedral
Cl geometry, that is, [As(S2 COMe)3 ] (44), or antiprismatic,
(37) that is, [As{S2 CN(CH2 CH2 OH)}3 ] (45) (Figure 13). These
14 ARSENIC: INORGANIC CHEMISTRY
C(15)
O(6) C(13)
O(2) N(3)
O(5)
C(11)
C(3) S(5)
S(4) O(3)
S(4)
S(6) C(8)
S(3)
C(9)
S(1) C(10)
S(5) As(1) C(6) N(2)
As C(3)
S(3) C(7)
C(5) S(2) C(1)
C(2) O(4)
S(2)
C(1)
O(3) N(1)
C(6) S(1)
S(6) O(1) C(2) O(1)
C(5)
C(4)
O(2)
(44) (45)
Figure 13 Homoleptic trisquelate arsenic complexes [As(S2 COMe)3 ] (44) and [As{(S2 CN(CH2 CH2 OH)}3 ] (45)46
C14 C7
C15 C6
S1 C16 C1 C8
S3 C13 S1 S4 C5
C1 C2 As1
C2 As1 P1
P1 C12
C11 C9
C10
S3
01 S4 S5 C16
C5 C3 C11
C3 C6 S2
S10
C4 C12
S2 C15
C4 C9 C7
C13 C14
C8
(46) (47)
Figure 14 X-ray structures of O(CH2 CH2 O)2 As(S2 PPh2 ) (46) and S(CH2 CH2 O)2 As(S2 PPh2 ) (47)47
ARSENIC: INORGANIC CHEMISTRY 15
stabilization in (49) comes from the delocalized 10 -electron, reaction between arsenic trichloride and the Grignard reagent
naphtalenic framework, which necessitates the employment prepared by acetylene (equation 31).
of AsS 4p 3p and AsN 4p 2p bonding. As a con-
sequence of p bonding in this arsenic cation the AsS and 2AsCl3 + 3IMgCCMgI As2 C6 + 3MgI2 + 3MgCl2 (31)
AsN distances (2.1536(15) and 1.776(4) A respectively) are
amongst the shortest known for AsIII species. The reaction is carried out in ether, out of which it separates
as a brown, amorphous solid. It is chemically resistant to both
N CH2Cl2 N
acids and bases. On heating, or by frictional action, the
As Cl + AlCl 3 + As AlCl4
(30)
S S material decomposes violently into the elements. Based on
(48) (49) this behavior it has been proposed that the compound is a
derivative of acetylene, that is, essentially arsenic acetylide.
Electron deficient coordinatively unsaturated thiaarsoli- The action of CNI on metallic arsenic gives a mixture of
dinium cations (50)49 and (51)50 have also been isolated. AsI3 and As(CN)3 , from which the iodide can be separated
These carbenic arsenium cations have been prepared by the by extraction with CS2 . The arsenic tricyanide hydrolyzes to
combination of the appropriate chlorodithiaarsolidine com- As2 O3 and HCN on exposure to moisture.
plex and a Lewis acid such as AlCl3 or GaCl3 that function as In a benzene solution the reaction between silver isocyanate
a halide abstractor. The reaction can be carried out in CH2 Cl2 and AsCl3 forms a precipitate of AgClAs(ONC)3 is obtained
as the solvent (Scheme 2). upon evaporation of the benzene in the form of a white,
X-ray crystallography revealed that the arsolidinium crystalline solid which melts at 97.1 C. The cyanate
cation (50) exists as a dimeric dication. The dimmer is Ag(CNO)3 is obtained by heating the isocyanate to 230 C
formed via intermolecular As S interactions (2.422(6) A). under reflux. At this temperature it isomerizes to the cyanate.
Addition of another equivalent of [(CH2 CH2 S2 )AsCl] to (50) Ag(CNO)3 decomposes rapidly in the presence of water
affords a bicyclic monocation, which can be viewed as the or acid.
Lewis complex (52) of the corresponding chloroarsolidine In a parallel manner, the reaction between Pb(CNS)3 and
[(CH2 CH2 S2 )AsCl], and the arsolidine cation (50).49 arsenic trichloride in CS2 , followed by filtration to remove
PbCl2 and evaporation of the solvent, gives As(CNS)3 . The
same product, a colorless, crystalline solid, can be prepared in
+
benzene solution from AgCNS and AsCl3 .
S S
As As
S S Cl
8 ARSENIC PNICTOGEN COMPOUNDS AND
(52) COMPLEXES BASED ON LIGANDS WITH
PNICTOGEN DONOR ATOMS
+
As
CH2Cl2
[(CH2CH2S2)AsCl] S S
(50)
+ ACl 3 +
ACl 4
As
CH2Cl2 S S
[S(CH2CH2S)2AsCl]
S
A = Al, Ga (51)
Scheme 2
16 ARSENIC: INORGANIC CHEMISTRY
(30 to 40 C). The white, amorphous solid is washed with The above mentioned nitride has also been synthesized
liquid ammonia in which it does not dissolve. This amide by passing a gaseous mixture of 10% nitrogen and
hydrolyzes readily to form arsenite. 90% argon through an electric arc between two arsenic
The amide begins to decompose at 0 C into the imide electrodes.
(equation 32). The decomposition is complete at 60 C. Alquilaminoarsines can be prepared by stepwise addition
of amines to arsenictrihalides in cooled ether solutions. The
2As(NH2 )3 As2 (NH)3 + 3NH3 (32) halogens are replaced successively by the alkylamino groups
as shown in Scheme 3.
The AsN bond is labile compared to the AsC, AsO,
The imide is a clear yellow solid which is much more or AsS bonds and this has been widely exploited in
resistant to hydrolysis than the amide and which possesses synthetic arsenic chemistry. For example, heating secondary
greater thermal stability. At 250 C it evolves ammonia and amines with tris(dialkylamino)arsines effects transamination
converts to the binary nitride (equation 33), which is a red- (equation 34).
orange solid that decomposes violently on heating.
C 6 H6
250 C As(NR2 )3 + 3HNMe2
As2 (NH)3 2AsN + NH3 (33) As(NMe2 )3 + 3HNR2 (34)
reflux
Et2O
AsCl3 + 2Me2NH [(Me2N)AsCl2] + [Me2NH2]Cl (a)
0 C
Scheme 3
As(OCNMe2)3
O
NMe2
As2O3
O
CO2
H2O
As(NMe2)3
RCHO
(no aH) RC(CH2OH)3
R
NMe2 HO (CH2)n OH
RCH + As 2O3
O O
NMe2 [{(CH2)nO)}AsNMe2] O As
CS2
{(CH2)nO)}As(SCNMe2)3
S
Scheme 4
ARSENIC: INORGANIC CHEMISTRY 17
N As
N
8.2 Arsenic Complexes Based on Ligands with Nitrogen N N
Donor Atoms
(53)
In the context of the preparation of novel arsenic
hypervalent species and the systematic study of ruffling in (2) hydrolysis (1) Hpy+Br3
porphyrins by the influence of axially coordinated ligands (36)
to a central element, complexes with arsenic and porphyrins +
OH
were isolated and fully characterized. The porphyrins used are
octaethylporphyrin, (OEP) and tetraphenylporphirin (TPP).
Reaction of OEPH2 or TPPH2 with AsCl3 in the presence of N As N OH
lutidine give [(OEP)AsCl] (53) or [(TPP)AsCl] (54) according N N
to equation (35).51
OH
(55)
Cl
Interestingly, the X-ray structure of the arsenicV fluoride
porphyrin complex, [(OEP)AsF2 ]+ PF6 shows an almost pla-
N As
N
OEPH2
N
nar conformation within the porphyrin core, which contrasts
N
the S4 ruffled conformation found for [(TPP)AsF2 ]+ PF6 .
A limited number of dicoordinate arsenium cations
(53)
(35)
with nitrogen based ligands have been isolated. Reaction
AsCl3
of the chlorodiazaarsenanes, [{(CH2 CH2 )(NMe)2 }AsCl] and
Cl
[{(CH2 CH2 CH2 )(NMe)2 }AsCl] with AlCl3 or GaCl3 in
N
Ph CH2 Cl2 afford the corresponding arsenium cations (56)48
Ph N As
N and (57)52 in good yield (Scheme 5).
TPPH2
N N Ph X-ray crystallography revealed a dimeric structure for
Ph cation (56), whereas cation (57) is monomeric in the solid
(54) state. The dimer in (56) is made with intermolecular As N
interactions (2.103(4) A).
Cations (56) and (57) react rapidly with 2,3-dimethyl-1,3-
butadiene in CH2 Cl2 to give the bicyclic cationic products (58)
After bromination and subsequent hydrolysis of (53) the and (59). The quantitive formation of (58) and (59) imply a
cationic arsenic complex (55) with arsenic in the 5+ oxidation concerted process, possibly a Diels Alder type cycloaddition
+
As
CH2Cl2
[{(CH2CH2(NMe)2)}AsCl] N N
(56)
+ ACl 3 +
ACl 4
As
CH2Cl2
[{(CH2CH2CH2(NMe)2}AsCl] N N
A = Al, Ga (57)
Scheme 5
18 ARSENIC: INORGANIC CHEMISTRY
O O Me Me
O As O As Me As COO Me As
O Me O
O O Me Me
Arsenate Methylarsenate Arseno-betaine Arseno-choline
(61) (62) (63) (64)
O
+
Me O
O
Me As CH2 O O O (CH2)nCH3
O
Me H H Me As P
O O
Me
H H O (CH2)nCH3
HO OH
O
Arseno-ribose Phosphatidyl-arseno-choline
(65) (66)
The simple oxides [AsO2 ] or [AsO4 ]3 (61) are slowly Methyl-carrier As(III)
organified to produce simple methylarsonic acids (62), more
complex betaines (63), cholines (64), sugar derivatives (65),
and lipids (66) (Figure 15). Reduction
Biological methylation of arsenic is effected via the
transfer of a carbocation, a process known as oxidative
methylation. The methyl transfer agent can vary from simple Carrier MeAs(V)
sulphonium salts, for example, S-adenosyl-S-methionine (67)
(equation 38) to specific methyltransferase enzymes. The
oxidation and methylation of the arsenite ion, [AsO3 ]3 , at [AsO4]3 [MeAsO3]2 [Me2AsO2] Me3AsO
physiological pH with (67) is illustrated in equation (38).
In solution under these conditions the major species is
Scheme 6
[H2 AsO3 ] (68). The cycle is completed trough the re-
reduction of new methylated arsenicalV by a range of
nonspecific reductants (Scheme 6). The organoarsenicals Studies of microbial systems have shown that the produc-
produced during biomethylation can be reduced by bacteria tion of trimethylarsine from the various methylarsonates is
with lipoic acid and by mammals with the ubiquitous more rapid than their respective thioarsinites, for example,
thiolate glutathione, as has been reported in in vitro Me2 AsSR, MeAs(SR)2 . However, there is a possible role for
studies.57 the thioarsinite in arsenic methylation. Studies on the binding
of arsenic to the methyltransferase enzyme suggest that prior
NH2 to the transfer of the methyl group the arsine oxide becomes
N N bound to a thiolate at the active site. In this way it is possible
to assist the binding of the softer arsenicIII substrate prior to
N
O CH3 N methylation and facilitate the release of the harder arsenicV
As OH
+ HOCCHCH2 S O species.54,57
+
O NH2 H H In general the toxicity of arsenic is more pronounced
OH H H
OH H with the lower oxidation states. The nature of the ligands
(68) (67) (38) around arsenic has also a profound effect on the overall
toxicity of the element. For example, dimethylarsonate,
NH2 [Me2 AsO2 ] has a LD50 = 700 mg kg1 while a richer
N
N oxygen environment in arsenate, [AsO4 ]3 (61) makes the
element much more toxic with a LD50 = 20 mg kg1 . Small
CH3 O N N inorganic species are more toxic than are organoarsenicals.
As
OH + HOCCHCH2 S O Libile ligands such as Cl or NH2 and the presence
O
OH NH2 H H of lone pairs would seem to increase toxicity, for
H
OH H
H example, [Me2 AsCl] with a LD50 = 5 mg kg1 . Quaternary
20 ARSENIC: INORGANIC CHEMISTRY
arsonium salts effectively protect the arsenic center giving 15. A. G. Massey, Main Group Chemistry, 2nd edn., John Wiley
relatively nontoxic and almost inert compounds, for example, & Sons, New York, 2000, Chap. 9.
[Me3 AsCH2 COO]. 16. M. M. Olmstead, P. P. Power, and G. A. Sigel, Inorg. Chem.,
Compounds that contain arsenicV in general are car- 1988, 27, 2045.
cinogenic. This is probably the result of its reduction to 17. B. Twamley, C. S. Hwang, N. J. Hardman, and P. P. Power,
arsenicIII . The thiophilicity of arsenicIII affect key enzymes, J. Organomet. Chem., 2000, 609, 152.
such as acetylcholine estereases, lipoic acid, and hemoglobin.
18. M. Brynda, G. Bernardinelli, C. Dutan, and M. Geoffroy, Inorg.
Long-term contact with the organometallic forms cause
Chem., 2003, 42, 6586.
hyperactivity, dizziness, speech, and psychological problems,
possibly linked to methylation which in turn facilitates its 19. W. A. Herrmann, B. Koumbouris, T. Zahn, and M. L. Ziegler,
transport across the blood-brain barrier.54 Angew. Chem., Int. Ed. Engl., 1984, 23, 812.
20. M. Driess and H. Pritzkow, Chem. Ber., 1994, 127, 477.
21. E. A. Ebsworth, R. O. Gould, R. A. Mayo, and M. Walkin-
shaw, J. Chem. Soc., Dalton Trans., 1987, 2831.
10 RELATED ARTICLES 22. A. H. Cowley, P. R. Harris, R. A. Jones, and C. M. Nunn,
Organometallics, 1991, 10, 652.
Antimony: Inorganic Chemistry; Arsenic: Organoarsenic 23. S. M. Godfrey, C. A. McAuliffe, A. G. Mackie, R. G. Prit-
Chemistry; Bismuth: Inorganic Chemistry; Phosphorus: chard, in Chemistry of Arsenic, Antimony and Bismuth,
Inorganic Chemistry. ed. N. C. Norman, Blackie Academic & Professional, London,
1998, Chaps. 3 and 4.
24. R. B. King, Inorganic Chemistry of the Main Group Elements,
VCH-Weinheim, 1994, Chap. 5.
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tions of Coordination Compounds, eds. Sir G. Wilkinson,
R. D. Guillard, and J. A. McCleverty, Pergamon Press, New 29. U. Muller and H. Sinnino, Angew. Chem., Int. Ed. Engl., 1989,
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3. D. Seyferth, Organometallics, 2001, 20, 1488. 30. C. A. Ghilardi, S. Mildollini, S. Moneti, and A. Orlandini, J.
4. W. E. Dasent, Inorganic Energetics, Cambridge University Chem. Soc., Chem. Commun., 1988, 1241.
Press, New York, 1988. 31. P. J. Jones, W. Beesk, G. M. Sheldrick, and E. Schawarzmann,
5. S. K. Pandey, A. Steiner, and H. Roesky, Inorg. Synth., 1997, Acta Crystallogr., 1980, B36, 439.
31, 148. 32. D. L. Hilderbrand, K. H. Kau, and R. D. Brittain, J. Chem.
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7. I. R. Grant, in Chemistry of Aluminum, Gallium, Indium and 33. A. Kutoglu, Z. Anorg. Allg. Chem., 1976, 419, 176.
Thalium, ed. A. J. Downs, Chapman & Hall, London, 1993, 34. E. Thilo, K. Hertzog, and A. Winkler, Z. Anorg. Allg. Chem.,
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Advanced Inorganic Chemistry, 6th edn., John Wiley & Sons, 36. E. Thilo, in Advances in Inorganic Chemistry and Radio-
New York, 1999, Chap. 10. chemistry, eds. H. J. Emeleus and A. G. Sharpe, Academic
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Oxford University Press, Oxford, 1998, Chap. 2. 35, 6682.
ARSENIC: INORGANIC CHEMISTRY 21
40. P. van Nuffle, A. T. H. Lenstra, and H. J. Teise, Acta 50. N. Burford, T. M. Parks, P. K. Bakshi, and T. S. Cameron,
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42. B. A. Borgias, G. G. Hardin, and K. N. Raymond, Inorg. 611, 200.
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Chem. Rev., 1984, 55, 207. Chem., 1996, 74, 2209.
44. C. Silvestru and I. Haiduc, Coord. Chem. Rev., 1996, 147, 53. C. J. Carmalt, V. Lomeli, B. G. McBurnett, and A. H. Cowley,
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Chem. Soc., 1992, 114, 8147.
Arsenic: Organoarsenic compounds that paralleled the heightened pursuit of synthetic
organic chemistry. This led to the development of synthetic
Chemistry pathways to the organohalo, organoamino, and tertiary arsines.
A significant upsurge in activity in synthetic organoarsenic
chemistry occurred with the discovery by P. Ehrlich in 1910
Larry K. Krannich & Charles L. Watkins that 3,3 -diamino-4,4 -dihydroxyarsenobenzene (Salvarsan
University of Alabama at Birmingham, Birmingham, AL, USA base) was an effective cure for syphilis. The next 33 years
witnessed the synthesis and biological testing of thousands
of new organoarsenic compounds and the development of
new synthesis strategies to heterocyclic compounds. With the
1 Introduction 1 advent of penicillin as a cure for syphilis in the 1940s, a
2 Fully Substituted Organoarsenic Compounds 2 lull occurred in the synthetic chemistry of organoarsenicals.
3 Organoarsines Containing AsH Bonds 4 The decreased activity and interest in main group chemistry
4 Organoarsenic Compounds Containing that occurred from the late-1960s to the mid-1980s brought
AsHalogen Bonds 5 few developments to the organometallic chemistry of arsenic,
5 Organoarsenic Compounds Containing AsGroup but saw their use as ligands in transition-metal chemistry.
13 Bonds 6
Beginning with the mid-1980s and the renewed interest in
6 Organoarsenic Compounds Containing AsGroup
14 Bonds 10 main group synthetic chemistry as it relates to materials
7 Organoarsenic Compounds Containing AsGroup chemistry, there has been a resurgence in research activity in
15 Bonds 11 organometallic arsenic chemistry. Much of this has occurred
8 Organoarsenic Compounds Containing AsO in the quest to develop viable single-source precursors
Bonds 16 for group 13 15 thin-film technologies. Thus, the areas
9 Related Articles 18 of arsenicaluminum, arsenicgallium, arsenicindium, and
10 References 18 multiple bonding in As/As and As/P systems have received
significant attention and many new bonding and As group 13
core systems have been explored. Synergistic, spectroscopic,
structural, and materials studies have occurred.
Glossary This review surveys the chemistry and reactivity of several
major classes of organometallic arsenic compounds that
Arsinic acid: general formula R2 As(O)OH, where R is an serve as the core of the field and represent those major
alkyl or aryl group areas of current research thrusts. General structural and
Arsinous acid: general formula R2 AsOH, where R is an recent spectroscopic data are discussed for each class of
alkyl or aryl group organometallic compound. Because of the great diversity of
Arsonic acid: general formula RAsO(OH)2 , where R is an organoarsenic compounds and limited space, not all areas
alkyl or aryl group of organoarsenic chemistry can be covered nor can all the
Arsonous acid: general formula RAs(OH)2 , where R is an synthetic strategies and reactivity be discussed. For example,
alkyl or aryl group we have chosen not to cover transition-metal complexes that
Diarsoxane: arsinous acid anhydride having the formula employ organometallic arsenic compounds as ligands, so we
(R2 As)2 O refer the reader to a book that provides a basic overview.1
Diarsene: general formula RAs=AsR , where R and R are Also, the heterocyclic chemistry of arsenic is not presented
bulky groups and the reader is referred to a book that surveys that field.2
Haloarsorane: general formula Rn AsX5n , where n = 1 3 For the same reason, we have not covered the biological and
Phosphaarsene: general formula RP=AsR , where R and R environmental aspects of organoarsenic chemistry. The latter
are bulky groups has been reviewed.3
In each section, we have referenced several books,414
monographs, and review articles that provide in-depth
coverage of the chemistry that is presented and give references
to the primary literature for developments in the field that have
1 INTRODUCTION taken place subsequent to the latest applicable review article.
We have focused on reviewing the primary synthetic routes
The organometallic chemistry of arsenic has a long history and reactivity that appear in previously published books and
that dates back to the synthesis and discovery in 1760 monographs and providing the reader with more in-depth
of the first organometallic compound, Me2 AsAsMe2 , by coverage of the latest developments.
L. C. Cadet de Gassicourt. During the late-1800s, there The physical, structural, and spectroscopic properties
was considerable interest in the synthesis of organoarsenic of organoarsenic compounds have been summarized in a
2 ARSENIC: ORGANOARSENIC CHEMISTRY
series of excellent reviews and monographs (1966,7 1968,8,9 routes to specific, symmetric tertiary arsines. Probably the
1970,6 1972,10,15 1975,5 1979,11 and 19854 ). In addition, most exhaustive coverage with references to the primary
annual reviews have provided key access to the literature literature for known synthetic routes to tertiary arsines is
(see cf. Journal of Organometallic Chemistry, Coordination provided by Dub,9,10 Cullen,7 Doak and Freedman,6 and
Chemistry Reviews, and Organometallic Chemistry, Royal Aylett.11
Society of Chemistry). The reader is referred to these Two practical synthetic methods have been reported for
sources for specific information on given organoarsenic the high-yield preparation of tertiary arsines. The reactions of
compounds. chlorodioxarsolane, OCH2 CH2 OAsCl, with aluminum alkyls,
Grignard reagents, organolithium, and dialkylzinc give high
yields of the fully substituted organoarsines.18 Grignard
reagents and aluminum alkyls readily react with As[NMe2 ]3
2 FULLY SUBSTITUTED ORGANOARSENIC to give tertiary arsines.19 The latter method is an adaptation of
COMPOUNDS the high-yield route to Me3 As20 that does not require using a
complexing agent for the Me3 As (equation 3).
2.1 Tricoordinate Arsenic 2As(NMe2 )3 + 3[Me3 Al]2 2Me3 As + 3[Me2 AlNMe2 ]2 (3)
Tertiary arsines comprise the most common class of Unsymmetric arsines of the type R2 AsR and RR R As
tricoordinate, fully organosubstituted arsenic compounds. are well known.311,16,21,22 The most common synthetic
Although there are a variety of methods for synthesizing CAs procedure involves alkylating the organomonohalo- or
bonds in tertiary arsines,411,16 the most extensively utilized organodihaloarsine with the desired Grignard or organolithium
routes involve the reaction of Grignard Reagents with arsenic reagent. Di-Grignard reagents have also been used to prepare
trihalides to give symmetric tertiary arsines (equation 1). The cyclic arsolanes.23 Good yields of heteroleptic tertiary arsines
yields of trialkylarsines are generally low to moderate and are obtained in the reaction of an organohalide with the
those of triarylarsines high. This reaction has been used to appropriate metal arsenide. The reaction of an organohalide
prepare the trineopentylarsine, As(CH2 CMe3 )3 .17 with a diarsine, R2 AsAsR2 , or a primary arsine, RAsH2 ,
is another route to unsymmetric arsines. The microbial
AsX3 + 3RMgX AsR3 + 3MgX2 (1) activity of molds acting on arsenicals in anthropogenic
and natural sources has also been exploited in producing
When the Grignard reagents react with primary and unsymmetric arsines.3,24,25 Et4 Pb and n-Bu3 Sb alkylate the
secondary haloarsines, As2 O3 , As2 S3 , trialkyl arsenites, and haloorganoarsines to give ethyl and butyl derivatives. Bn2 Hg
arsenic thioacid esters, the resulting tertiary arsines are gives a quantitative yield of Me2 AsBn when Me2 AsI is used,
often contaminated with other arsenicals. Lithium alkyls are but a lesser yield and by-product contamination result when
frequently used when the Grignard is difficult to obtain, but Me2 AsH is alkylated.26 By capitalizing on the reactivity of
side-products serve as contaminants. Although the reaction Me2 AsNMe2 toward Grignard reagents and aluminum alkyls,
times are long and yields depend upon the alkyl group, a general protocol has also been developed to the Me2 AsR
aluminum alkyls also effectively alkylate As2 O3 and arsenic arsines (equation 4).27
trihalides. The Wurtz Fittig reaction is seldom used in
2Me2 AsNMe2 + 2Et3 Al 2Me2 AsEt + [Me2 NAlEt2 ]2 (4)
synthesizing trialkylarsines, but has been utilized to prepare
cyclic arsines (equation 2).
Dinuclear arsines containing a bridging methylene unit,
C6 H4 (CH2 Br)2 + MeAsCl2 + 4Na (2) R2 AsCH2 AsR2 , have been prepared from the parent haloarsine
using RLi.28 With PhCCLi, cleavage of the AsCH2 As
C6 H4 (CH2 )2 AsMe + 2NaCl + 2NaBr
backbone occurs and As(CCPh)3 is isolated.
Tertiary arsines are readily oxidized with common
Zinc and mercury dialkyls have found limited application oxidizing agents (H2 O2 , KMnO4 ) to the arsine oxide.
in alkylating arsenic trihalides. The advantage with the zinc Oxidation of the alkyl derivatives with H2 O2 or HgO gives
dialkyls is that they give very pure tertiary arsines even the trialkylarsine oxide R3 AsO, but air oxidation produces the
though the arsines are obtained in low yields. Numerous other dialkylarsinic acids, R2 As(O)OH. With sulfur and selenium,
methods that employ redistribution of alkylhaloarsines at the trialkylarsines are oxidized to the corresponding sulfide
elevated temperatures, reduction of arsonium salts, pyrolysis and selenide. They readily form adducts with diborane,
of arsonium salts and arsine oxides, reaction of arsenic halides aluminum alkyls, AlCl3 , and gallium alkyls.29 Their reactions
with diazoalkanes, reaction of SnR4 and alkyl radicals with with NH2 Cl, MeNHCl, and Me2 NCl produce the respective
elemental arsenic, alkylation of diarsines and aminoarsines aminoarsonium chlorides (equation 5).30,31
with organolithium, or the action of Penicillium brevicaule on
bread that contains sodium cacodylate have provided unique Et3 As + Me2 NCl [Et3 AsNMe2 ]Cl (5)
ARSENIC: ORGANOARSENIC CHEMISTRY 3
Et3 As reacts with AsCl3 in n-pentane to give a quantitative Barriers to inversion of about 200 kJ mol1 have been
yield of the sublimable dimer [Et3 AsAsCl3 ]2 ,32 which determined for tertiary arsines, both by experimental and
disproportionates above its melting point to a mixture semiempirical quantum mechanical calculations (see Semi
of Et2 AsCl and EtAsCl2 . Tertiary arsines react with a Empirical Theoretical Methods).5,11 The inversion barriers in
stoichiometric amount of halogen to form the R3 AsX2 species arsines are considered to be the maximum for the group 15
(equation 6). These disproportionate on heating to give the elements, with values being about 60 kJ mol1 higher than for
haloarsine and an alkyl halide (equation 7). This can serve corresponding phosphines.11 For partially and fully substituted
as a convenient synthetic route to the dialkylhaloarsines. silylarsines,11,37 the inversion barrier at arsenic decreases as
Although the tertiary arsines have been extensively used as more silicon atoms are directly attached.
ligands in transition-metal complexes,1,911 this chemistry will
not be treated here as part of the chemistry of organometallic
arsenic compounds. 2.2 Dicoordinate Arsenic
shifts compared with the corresponding tertiary arsines. gives low yields of primary arsines in the reduction of
Similar multinuclear NMR data have been summarized for alkyldichloroarsines. In the latter case, the formation of
Ph4 As+ X .41,42 AlAs bonded species is thought to significantly lower the
Deprotonation of arsonium salts [R3 AsCHR2 ]X with arsine yields, but with the bulky Me3 SiCH2 and Me3 CCH2
phenyllithium or -sodium in liquid ammonia yields the groups, both the primary and secondary arsine are readily
ylides R3 As=CR2 (see Ylide). Me3 As=CH2 can be syn- obtainable through the reduction of the respective haloarsine
thesized from Me3 As by first quaternizing the arsine with LiAlH4 .46,49,50 Similarly, 2,6-(Me2 NCH2 )2 C6 H3 AsCl2 is
with Me3 SiCH2 Cl, then using BuLi to deprotonate the easily reduced to the primary arsine using LiAlH4 .51 LiBH4 is
arsonium salt, and finally removing the Me3 Si by the excellent for reducing PhAsCl2 . Although a complex mixture
reaction with Me3 SiOH. The first mixed P/As double of alkylated arsines and AsH3 is obtained when LiAlH4 is
ylide, Ph2 (Me)P=C=As(Me)Ph2 , was prepared from the used to reduce vinylchloroarsines, good yields (ca. 60%)
reaction of the arsonium salt [Ph2 (Me)PCH2 As(Me) of the respective primary and secondary vinyl arsines are
Ph2 ](SO3 F)2 with NaNH2 in liquid ammonia.43 obtained using butylstannane.52 Benzene reacts with AsCl3
The 1 H NMR chemical shift for the CH2 group in in the presence of AlCl3 to give a mixture of Ph2 AsH and
Me3 As=CH2 is to high field, above TMS. This suggests PhAsH2 . The alkylarsines are also prepared by the reaction
the importance of the canonical form Me3 As+ CH2 in of an alkyl halide with NaAsH2 . When potassium diaryl- or
contributing to the structure.4,5,11,15 arylalkylarsenide is reacted with water, a high yield of the
secondary arsine results. MeAsHCl can be synthesized by
2.4 Pentacoordinate Arsenic reacting MeAsCl2 with EtSbH2 (equation 12).53
A limited number of pentaorganoarsoranes, AsR5 , are 2MeAsCl2 + EtSbH2 2MeAsHCl + EtSbCl2 (12)
known.4,5,44,45 Me5 As is prepared in high yield by the reaction
of methyllithium with Me3 AsCl2 . On the other hand, Ph5 As Although primary and secondary arsines do not react
is formed by reacting phenyllithium with either Ph3 AsO, with water, they are easily oxidized by oxygen.46,911,54
[Ph4 As]Br, or the tosylimine Ph3 As=NSO2 C6 H4 Me. A redox For this reason, oxygen must be rigorously excluded in their
reaction occurs when (Me3 SiCH2 )3 As is mixed with AsCl3
synthesis. In the presence of oxygen, primary arsines give the
to give (Me3 SiCH2 )3 AsCl2 and elemental arsenic.46 A recent
cyclopolyarsines (equation 13), but in a stoichiometric excess
review article45 provides references on the synthesis and
of oxygen yield the arsonic acids RAs(O)(OH)2 (equation 14).
reactivity of several other arsoranes.
The hydrogens are easily replaced by treatment with sodium,
A trigonal bipyramidal solution structure (see Trigonal
organolithium, or Grignard reagents to give organoarsenides
Bipyramidal) has been proposed for Me5 As from vibrational
of the type R2 AsM, RAs(H)M, and RAsM2 (M = Li, Na, K,
and 1 H NMR studies.11,44,45 1 H NMR, vibrational, and crystal-
MgX), which are useful in the synthesis of tertiary, ditertiary,
structure data indicate that Ph5 As is trigonal bipyramidal in
and tritertiary arsines.
solution and the solid state.47,11,44,45
10MeAsH2 + 5O2 2(MeAs)5 + 10H2 O (13)
2MeAsH2 + 3O2 2MeAs(O)(OH)2 (14)
3 ORGANOARSINES CONTAINING AsH BONDS
Both the primary and secondary arsines are strong reducing
3.1 Primary and Secondary Arsines agents and undergo facile oxidization with the halogens,
aliphatic and aromatic aldehydes, haloarsines, chloramine
Organoarsines containing the AsH bond are limited to the and dimethylchloramine, SO2 Cl2 , and Me3 PbOMe to give
primary and secondary organoarsines.4,5,7,911,47 Both the alkyl the corresponding diarsines or cyclopolyarsines.46,911,54 In
and aryl derivatives are usually synthesized by the reduction the absence of triethylamine or with higher stoichiometric
of the arsinous acid [R2 AsOH], arsonic acid [RAsO(OH)2 ], amounts of the halogen, halogenation of the primary and
arsinic acid [R2 As(O)OH], or organohaloarsines [RAsX2 or secondary arsines leads to substitution and formation of the
R2 AsX] with powdered zinc or zinc amalgam and hydrochloric dihalo- and haloarsine (equations 15 18).
acid (equations 10 and 11). Reduction of (Me3 SiCH2 )2 AsCl
with Zn/Cu amalgam in a hydrochloric acid/THF solution 6PhAsCl2 + 12Ph2 AsH (PhAs)6 + 6(Ph2 As)2 + 12HCl (15)
gives a high yield of the secondary arsine and avoids the
5MeAsH2 + 5H2 NCl (MeAs)5 + 5NH4 Cl (16)
formation of the diarsine.48
6PhAsH2 + 6SO2 Cl2 (PhAs)6 + 12HCl + 6SO2 (17)
RAsO(OH)2 + 3Zn + 6HCl RAsH2 + 3ZnCl2 + 3H2 O (10)
2Me2 AsH + Cl2 + 2Et3 N Me2 AsAsMe2 + 2Et3 NHCl (18)
R2 AsCl + Zn + HCl R2 AsH + ZnCl2 (11)
Reduction of the dialkylchloroarsines with LiAlH4 MeAsH2 reacts with Me2 AsAsMe2 to give (MeAs)5 and
affords an alternative route to the secondary arsines, but Me2 AsH.55 With Me2 AsNMe2 , the products are (MeAs)5 ,
ARSENIC: ORGANOARSENIC CHEMISTRY 5
Me2 AsH, and Me2 NH.56 Other primary arsines easily react in the presence of a hydrogen halide and a trace of
with (MeAs)5 to generate the respective cyclopolyarsine KI.47,911,77 Because haloarsines are in equilibrium with
(RAs)n , where n = 5 or 6, and MeAsH2 .57,58 Me2 AsH their respective arsonous or arsinous acids in aqueous
reacts with Me2 AsNMe2 (and its BH3 adduct) to produce solution, they can be prepared by the addition of excess
Me2 AsAsMe2 .59 Secondary arsines also react with symmetric hydrohalic acid to the respective acids (equation 20). Highly
diarsines to give mixtures of unsymmetric and symmetric pure alkyldichloroarsines are obtained by heating the
diarsines (equation 19).60 The analogous reaction of Me2 AsH 10-alkyl-5,10-dihydrophenarsazines with hydrogen chloride
with Et2 PPEt2 yields a mixture of Et2 PH, Me2 AsAsMe2 , (equation 21). Cleavage of the AsN bond in aminoarsines
and Me2 AsPEt2 .60 Ph2 AsH will cleave the SnN bond in with hydrogen halides provides another route to the haloarsines
Me2 NSnMe3 to give Ph2 AsSn(Me3 )3 .61 (equation 22).
3R2 AsH + 2R 2 AsAsR 2 R2 AsAsR2 + R2 AsAsR 2 + 3R 2 AsH RAs(OH)2 + 2HX RAsX2 + 2H2 O (20)
(19) H
N
C6H4 C6H4
The reaction of Me2 AsH with diborane produces Me2 AsH As + 3HCl MeAsCl2 + [Ph2NH2]+Cl
BH3 . When the reaction is carried out at 50 C, [Me2 AsBH2 ]3
Me
and [Me2 AsBH2 ]4 are formed. The reaction of Me2 AsH, (21)
(t-Bu)2 AsH, or Ph2 AsH with aluminum alkyls proceeds +
EtAs(NMe2 )2 + 4HCl EtAsCl2 + 2[Me2 NH2 ] Cl (22)
through a 1,2-elimination reaction to yield arsinoalanes of
the following type: [Me2 AlAsMe2 ]3 ,62,63 [Me2 AlAsPh2 ]3 ,64
[Me2 AlAs(t-Bu)2 ]2 ,65 and [Et2 AlAs(t-Bu)2 ]2 .66 Other sec- Redistribution reactions that involve heating the appropri-
ondary arsines react in an analogous fashion with organogal- ate stoichiometric mixtures of the tertiary arsines with AsCl3
lanes and organoindanes to give [Me2 GaAs(i-Pr)2 ]3 ,67 produce the mono- and dihaloarsines (equations 23 and 24).
[Ph2 GaAs(CH2 SiMe3 )2 ]2 ,48 [Me2 GaAs(CH2 CMe3 )2 ]2 ,50 [(i- Disproportionation of a dihaloarsorane at high temperatures
Pr)2 GaAs(i-Pr)2 ]2 ,68,69 [Me2 InAsMe2 ]3 ,62 [Me2 InAsPh2 ]2 ,70 serves as a convenient synthetic route to the dialkylhaloarsines
and [Me2 InAs(t-Bu)2 ]2 .65 With primary arsines, the reac- (equation 25).
tions proceed to give uncharacterized oligomers, except
when there are bulky substituents on arsenic or gal- 2AsR3 + AsCl3 3R2 AsCl (23)
lium. For example, the reaction of Me3 CCH2 AsH2 with AsR3 + 2AsCl3 3RAsCl2 (24)
Me3 Ga gives [Me2 GaAs(H)CH2 CMe3 ]n 50 and that of PhAsH2 2RAsX2 R2 AsX + AsX3 (25)
with [Me3 SiCH2 ]3 Ga produces the unique galliumarsenic
cluster compound (PhAsH){[Me3 SiCH2 ]2 Ga}(PhAs)6 [Me3 -
Alkylation of AsX3 using organomercury and tetraalkyl-
SiCH2 Ga]4 (see Section 5).71
lead works well for those haloarsines that are difficult to
Vibrational and NMR spectroscopic techniques have been
prepare by the more drastic conditions of the dispropor-
employed to investigate general conformational properties
tionation and redistribution reactions. Although incomplete
in primary and secondary organoarsines, as well as the
alkylation of AsCl3 with aluminum alkyls gives haloarsines,
determination of AsH bond strength and lability.6,15,37,72
these usually are obtained as mixtures of the mono- and
Molecular orbital calculations (see Molecular Orbital Theory)
dihaloarsines with the tertiary arsines. Because complete
have also been published on a series of RAsH2 .73 There
alkylation of AsCl3 does not generally occur with the Grig-
has been considerable interest in the characterization of
nard reagents, this method is only used in a few special
organoarsines, including 13 C NMR data.49,50,55,56,58,60,74,75
cases. The reaction of organohalides at moderate tempera-
Most of this interest is due to the assessment of their possible
tures with elemental arsenic in the presence of copper yields
use as replacements for AsH3 in the production of gallium
mixtures of R2 AsX, RAsX2 , R3 As, AsX3 , and As2 X4 . The
arsenide thin films and in the synthesis of precursors for group
salt elimination reaction has been used in the recent synthesis
13 15 semiconductors.76
of (eta-C5 Me5 )2 AsCl from AsCl3 and LiC5 Me5 .78 Vinyl-
haloarsines have been prepared in high yields by the reaction
of AsCl3 with 1:1 and 1:2 mol ratios of vinylstannane.51
Numerous other methods are employed to prepare specific
4 ORGANOARSENIC COMPOUNDS CONTAINING
haloarsines and references to the primary literature for these
AsHALOGEN BONDS
can be found in reviews.47,911,77 In general, the chloro- and
bromoarsines are the most easily synthesized and are used
4.1 Mono- and Dihaloarsines in halogen exchange reactions to prepare the fluoro- and
iodoarsines (equation 26).
The haloarsines are most commonly prepared from the
reduction of the arsonic or arsinic acids by sulfur dioxide Ph2 AsCl + AgF Ph2 AsF + AgCl (26)
6 ARSENIC: ORGANOARSENIC CHEMISTRY
The organohaloarsines are very reactive species and are X-ray studies have established that the neopentyl derivative
commonly used to prepare heteroleptic tertiary arsines (see As(CH2 CMe3 )Br2 is trigonal bipyramidal.17
Section 2), primary and secondary arsines (see Section 3), and
aminoarsines and catenated arsines (see Section 7.3). They
easily hydrolyze to their respective arsonous and arsinous
acids (equation 27) and are oxidized in air to the corresponding 5 ORGANOARSENIC COMPOUNDS CONTAINING
arsonic and arsinic acids (equation 28). AsGROUP 13 BONDS
bond distances and C(H)AlC(H) bond angle parameters are Table 2 AsGa bonded compounds synthesized after 1985
useful in predicting adduct stability. Four cycloarsinoalane
dimers have been characterized by single-crystal X-ray anal- AsGa bonded compounds Method of preparation
ysis. In each case, the (AlAs)2 ring is planar with a distorted
tetrahedral geometry about both the Al and As atoms and the Et3 AsGaMen (C6 F5 )3n Direct109
[ClMe2 GaAsEt2 ]2 CH2 Direct110
endocyclic angle subtended at arsenic is larger than at alu- (t-Bu)2 (H)AsGa(i-Pr)3 Direct69
minum. The AlAs bond distances and the AlAsAl and the (Me3 Si)3 AsGaPh3 Direct111
AsAlAs angles are as follows: [Me2 AlAs(SiMe3 )2 ]2 96 (tri- (Me3 Si)3 AsGa(Cl)(CH2 CMe3 )2 Direct112
clinic: 2.536 A, 91.71 , 88.29 ); [Et2 AlAs(SiMe3 )2 ]2 99 (mon- Ph3 AsGaI3 Direct113
oclinic: 2.535 A, 91.01 , 88.99 ); [(i-Bu)2 AlAs(SiMe3 )2 ]2 96 (p-MeOC6 H4 )3 AsGaI3 114
(Et3 As)2 Ga2 I4 114
(monoclinic: 2.550 A, 92.23 , 87.77 ); [Et2 AlAs(t-Bu)2 ]2 66 [(THF)Br2 Ga]3 As Dehalosilylation115
(monoclinic: 2.567 A, 94.54 , 85.46 ). For the base- {[2,4,6-(i-Pr)2 C6 H2 ]2 Ga}2 AsPh Salt elimination116
stabilized monomeric aminoalanes, the AlAs bond dis- (Ph3 Si)[(Me3 Si)2 CH]AsGa(t-Bu)2 Salt elimination117
tances are as follows: Me2 AlAs(SiMe3 )2 dmap, 2.470 [(Mes)2 As]3 Ga Salt elimination97,118
and 2.472 A;104 Et2 AlAs(SiMe3 )2 dmap, 2.473 A;104 and (t-Bu2 As)3 Ga Salt elimination65,119
[(Me3 Si)2 As]3 Ga 120
(Me3 Si)2 AsAlH2 NMe2 , 2.438 A.103 The borazine analogue, {[(Me3 SiCH2 )2 As]3 Ga}2 Salt elimination121
[Mes AlAsPh]3 , exhibits a nonplanar boat conformation with [(Me3 SiCH2 )2 AsGaMe2 ]2,3 Dehalosilylation122
little or no arsenic lone pair delocalization and bond lengths [(Me3 CCH2 )2 AsGaMe2 ]2 1,2-elimination50
consistent with Al As single bonds.101 [(Me3 SiCH2 )2 AsGaPh2 ]2 1,2-elimination48
[Me3 SiCH2 (H)AsGaPh2 ]3 1,2-elimination49
[(Me3 Si)2 AsGa(CH2 CMe3 )2 ]2 Salt elimination112
5.3 AsGa Bonded Compounds [(Me3 Si)2 AsGaH2 ]3 Dehydrosilylation123
[(Me3 Si)2 AsGa(CH2 SiMe3 )2 ]2 Salt elimination124
Prior to 1986, there were very few known and characterized [(Me3 Si)2 AsGa(t-Bu)2 ]2 Salt elimination125
[(Me3 Si)2 AsGaPh2 ]2 Salt elimination126,127
AsGa compounds.29,107,108 Since that time, there has been [(Me3 Si)2 AsGaMe2 ]2 Dehalosilylation128
a significant increase in the number of synthesized and fully (Me3 Si)2 AsGa(C5 Me5 )2 Salt elimination129
characterized AsGa species. Table 2 contains a listing of [(t-Bu)2 AsGaMe2 ]2 Salt and
the organometallic AsGa bonded compounds that have been 1,2-elimination65,119
[(t-Bu)2 AsGaEt2 ]2 130
synthesized from 1986 to 2003 and indicates their method of
[(t-Bu)2 AsGaBu2 ]2 Salt elimination119
synthesis. [(t-Bu)2 AsGa(allyl)2 ]2 Salt elimination131
These compounds can be classified according to the AsGa [(t-Bu)2 AsGa(benzyl)2 ]2 Salt elimination131
bonding nucleus as simple AsGa adducts, twist-boat con- [(t-Bu)2 AsGa(vinyl)2 ]2 Salt elimination131
formation (AsGa)3 rings, planar or nonplanar (AsGa)2 [(t-Bu)(H)AsGa(t-Bu)2 ]3 1,2-elimination98
[(t-Bu)2 AsGa(CH2 )4 ]2 Salt elimination132
rings, nonplanar GaAsGaX rings (X = halogen), pyrami-
(t-Bu)2 AsGa(t-Bu)2 Salt elimination133
dal Ga3 As gallanoarsines, and planar As3 Ga arsinogallanes. [H2 AsGa(t-Bu)2 ]3 1,2-elimination134
Much of the synthesis activity is a consequence of the search [(i-Pr)2 AsGaMe2 ]3 1,2-elimination67
for volatile, single-source, gallium arsenide precursors that [(Me3 SiCH2 )2 AsGaCl2 ]3 Dehalosilylation97
will not incorporate AsC bonds into thin films grown from [(Me3 SiCH2 )2 AsGaBr2 ]3 Dehalosilylation135,136
OMCVD processes.141 There has been a judicious variation [(Me3 SiCH2 )2 AsGaClMe]2,3 Dehalosilylation135
[(Me3 SiCH2 )2 AsGaClPh]2,3 Dehalosilylation135
of substituents and the application of three general synthe- [{(Me3 SiCH2 )2 As}2 GaCl]2 Dehalosilylation97
sis methodologies, other than direct adduct formation, to [{(Me3 SiCH2 )2 As}2 GaBr]2 Dehalosilylation135
give compounds that contain these AsGa linkages: 1,2- [{(Me3 SiCH2 )2 As}2 GaPh]2 122
elimination (equation 38), salt elimination (equation 39), and (t-Bu)2 GaAs(SiMe3 )2 Ga(t-Bu)2 Cl Direct125
dehalosilylation (equation 40). Ph2 GaAs(SiMe3 )2 Ga(Ph)2 Cl Dehalosilylation126,127
Ph2 GaAs(SiMe3 )2 Ga(Ph)2 Br Dehalosilylation127
2(Me3 SiCH2 )2 AsH + 2GaPh3 (Me3 SiCH2 )2 GaAs(SiMe3 )2 Ga- Dehalosilylation124
(CH2 SiMe3 )2 Cl
[(Me3 SiCH2 )2 AsGaPh2 ]2 + 2PhH (38)
(Me3 CCH2 )2 GaAs(SiMe3 )2 Ga- Dehalosilylation112
2(Me3 Si)2 AsLi + 2ClGa(CH2 SiMe3 )2 (CH2 CMe3 )2 Cl
[(t-Bu)2 GaAsC6 H3 (CH2 NMe2 )- Salt elimination137
[(Me3 Si)2 AsGa(CH2 SiMe3 )2 ]2 + 2LiCl (39)
CH2 NMe2 ]2
(Me3 SiCH2 )2 AsSiMe3 + 2GaBr3 Ph2 GaCl(Ph)2 Ga(Me3 Si)As(CH2 )3 - Dehalosilylation138
[(Me3 SiCH2 )2 AsGaBr]2 + 2Me3 SiBr (40) As(SiMe3 )Ga(Ph)2 ClGaPh2
(PhAsH)[(Me3 SiCH2 )2 Ga](PhAs)6 - 1,2-elimination71
(Me3 SiCH2 Ga)4
Dehydrosilylation occurs in the reaction of H3 GaNMe3 [(C4 Me4 As)4 Ga]Li(THF)4 Salt elimination139
with As(SiMe3 )3 to provide an efficient route to [(Me3 Si)2 - Ga2 {As(Si(i-Pr)3 )}4 Salt elimination140
AsGaH2 ]3 .123
ARSENIC: ORGANOARSENIC CHEMISTRY 9
The first example of an arsinogallane that contains the A few studies have been carried out on the arsinogallanes
H2 As moiety, [(t-Bu)2 GaAsH2 ]3 , has been prepared in quan- as potential single-source GaAs precursors. Pyrolysis of
titative yield from the reaction of t-Bu3 Ga with AsH3 .134 (t-Bu)2 GaAs(t-Bu)2 ,133 [(t-Bu)2 GaAsH2 ]2 ,134 [Me2 GaAs(t-
Although the 1,2-elimination route was first used to pre- Bu)2 ]2 ,130 and [Et2 GaAs(t-Bu)2 ]2 130 gives polycrystalline
pare [Me2 AsGaMe2 ]3 62 and [Me2 AsGaPh2 ]2 ,70 as the steric GaAs. GaAs films have been obtained from [Me2 GaAs(t-
bulk of the substituents increases the utility of this approach Bu)2 ]2 142,143 and [Et2 GaAs(t-Bu)2 ]2 130,143 using these as
becomes impractical to prepare arsinogallanes. For example, single sources in a chemical beam epitaxy reactor. [(t-
the reaction of (t-Bu)2 AsH with Ga(i-Pr)3 gives only the Bu)2 As]3 Ga also produces thin films, which are n-type.143
simple adduct (t-Bu)2 AsHGa(i-Pr)3 69 and the reaction of The pyrolysis mechanism of Et3 AsGaMen (C6 F5 )3n 109 and
PhAsH2 with Ga(CH2 SiMe3 )3 yields the AsGa cluster com- [ClR2 GaAsEt2 ]2 CH2 110 (R = Me, Et) has been studied using
pound (PhAsH){[Me3 SiCH2 ]2 Ga}(PhAs)6 [Me3 SiCH2 Ga]4 .71 mass spectrometry in GaAs vapor-phase epitaxy.
Salt elimination and dehalosilylation have now become the Mono(arsino)gallanes can occur as monomers, dimers,
preferred synthetic routes to the nonadduct systems (see or trimers (see Table 2). More sterically demanding
Table 2).122 substituents enhance monomer or dimer formation.
Arsenichalogen mixed-bridge compounds, R2 GaAs- In three instances,122,135 dimer/trimer equilibrium has
(SiMe3 )2 Ga(R)2 X, have been prepared by dehalosilylation that been detected by NMR spectroscopic techniques.
involves As(SiMe3 )3 and R2 GaX (R = Ph, X = Cl, Br; R = (Me3 Si)2 AsGa(C5 Me5 )2 129 and (t-Bu)2 AsGa(t-Bu)2 133 are
Me3 SiCH2 , Me3 CCH2 , X = Cl) (equation 41).112,122,124,126,127 monomeric. The following R2 AsGaR2 arsinogallanes are
The dimeric arsinogallanes also react with halogallanes dimeric: R = Me3 CCH2 , R = Me;50 R = Me3 SiCH2 , R =
to yield the mixed-bridge species (equation 42), which Ph;48 R = Me3 Si, R = CH2 CMe3 ,112 CH2 SiMe3 ,124 Me,128
can be reconverted to the respective dimer by reac- t-Bu,125 or Ph;126,127 R = t-Bu, R = Me,65,119 Et,130 or
tion with the LiAs(SiMe3 )2 .112 Reaction of the mixed- n-Bu.119 In each case, available X-ray data indicate
bridge Ph2 GaAs(SiMe3 )2 Ga(Ph)Cl with LiP(SiMe3 )2 leads planar (GaAs)2 rings. Trimers have been reported
to substituent transfer at both Ga and As to yield the for Me3 SiCH2 (H)AsGaPh2 ,49 (t-Bu)(H)AsGa(t-Bu)2 ,98
adduct Ph3 GaAs(SiMe3 )3 , which can also form from H2 AsGa(t-Bu)2 ,134 (i-Pr)2 AsGaMe2 ,67 and (Me3 SiCH2 )2 -
the direct reaction of Ph3 Ga and As(SiMe3 )3 .111 An AsGaX2 (X = Cl,97 Br135,136 ). X-ray studies67,136 have
As2 Ga2 ring that is intramolecularly base-stabilized, [(t- indicated that the (GaAs)3 ring exists in a distorted or
Bu)GaAsC6 H3 (CH2 NMe2 )(CH2 NMe2 )]2 , has been prepared twisted-boat conformation. Trimers of H2 GaAs(SiMe3 )2 exist
by treating t-BuGaCl2 with Li2 AsC6 H3 (CH2 NMe2 )2 .137 as flattened (GaAs)3 rings.123
The bis(arsino)gallanes [(Me3 SiCH2 )2 As]2 GaX (X =
(Me3 Si)3 As + 2Ph2 GaCl Ph2 GaAs(SiMe3 )2 GaPh2 Cl + Me3 SiCl Cl,97 Br135 ) are dimers with a planar (GaAs)2 ring and
(41) crystallize135 in the trans configuration. The tris(arsino)-
[(Me3 Si)2 AsGa(CH2 CMe3 )2 ]2 + 2(Me3 CCH2 )2 GaCl gallane (Mes2 As)3 Ga is nearly trigonal planar97,118 and
2(Me3 CCH2 )2 GaAs(SiMe3 )2 Ga(CH2 CMe3 )2 Cl (42) [(Me3 Si)2 As]3 Ga is trigonal planar,120 while (t-
Bu2 As)3 Ga has distorted pyramidal geometry.65,119 However,
The salt elimination reaction has been employed to [(Me3 SiCH2 )2 As]3 Ga is dimeric121 with a nonplanar (GaAs)2
prepare two volatile monomeric arsinogallanes with bulky ring.
substituents on both As and Ga (equations 43 and 44).129,133 The tris(gallyl)arsines As[GaBr2 (THF)]3 and Ph3 Si-
Three sterically hindered trisarsinogallanes, (Mes2 As)3 Ga,118 [(Me3 Si)2 CH]AsGa(t-Bu)2 have a pyramidal Ga3 As
{[(Me3 SiCH2 )2 As]3 Ga}2 ,121 and (t-Bu2 As)3 Ga,65,119 have skeleton.115 From X-ray data, the halogen mixed-bridge
been synthesized by salt elimination in the reaction of species contain a GaAsGaX ring that may be planar112,125
the lithium arsenide and the respective chlorogallane. or nonplanar,124,126,127 depending on the steric requirements
Dehalosilylation is an alternative route to the mesityl of the substituents.122 Ga2 {As[Si(i-Pr)3 ]4 } has a structure sug-
compound.97 [(Me3 Si)2 As]3 Ga has been isolated as one gesting galliumarsenic double bonds involving the exocyclic
of the products from the reaction of LiAs(SiMe3 )2 and As moieties bound to the Ga atoms in the planar Ga2 As2
[Cl2 GaP(SiMe3 )2 ]2 .120 ring.140 The reader is referred to two excellent reviews
on the characterization of these and other galliumarsenic
(t-Bu)2 AsLi + ClGa(t-Bu)2 (t-Bu)2 AsGa(t-Bu)2 + LiCl (43) compounds.122,141
(Me3 Si)2 AsLi + ClGaCp 2 (Me3 Si)2 AsGaCp 2 + LiCl (44)
5.4 AsIn Bonded Compounds
The first arsinogallate [(C4 Me4 As)4 Ga]Li(THF)4 has been
reported.139 It is synthesized from the lithium salt of Prior to 1994, very few AsIn bonded compounds were
the [C4 Me4 As] anion, which is a permethylated arsole known. In the intervening 10 years, salt elimination, 1,2-
derivative, and GaCl3 . Li(THF)2 Ga2 {As[Si(i-Pr)3 ]3 }4 is elimination, and dehalosilylation preparative routes have been
synthesized by an analogous route.140 extended to AsIn chemistry. Table 3 contains a listing of the
10 ARSENIC: ORGANOARSENIC CHEMISTRY
Table 3 Known AsIn bonded compounds (SiMe3 )2 ]2 in a 1:1 mol ratio yields (Me3 SiCH2 )InAs-
(SiMe3 )2 In(CH2 SiMe3 )2 P(SiMe32 )2 , which has a four-
AsIn bonded compounds Method of preparation membered planar (InAsInP) ring.151 Et3 In reacts with
[Me2 AsInMe2 ]3 1,2-elimination62 H2 AsSi(i-Pr)3 to yield the [EtInAsSi(i-Pr)3 ]4 , which
[Ph2 AsInMe2 ]2 1,2-elimination70 exhibits a heterocubane structure.147 Other InAs cage
[(t-Bu)2 AsInMe2 ]2 1,2-elimination65 type compounds have resulted by reacting MesInCl2 and
[(Me3 Si)2 AsInEt2 ]2 1,2-elimination146 InCl3 with the dilithium arsenide, (BuAsLi)2 (t-Bu), in a
[EtInAsSi(i-Pr)3 ]4 1,2-elimination147 4:2:4 mol ratio to produce (MesInCl)4 (InCl)2 [As(t-Bu)]4 .
[Ph2 InAs(SiMe3 )2 ]2 Dehalosilylation145
[(Me3 Si)2 AsIn(CH2 SiMe3 )2 ]2 Dehalosilylation144
Using Me2 InCl and MeInCl with (BuAsLi)2 (t-Bu) in a
(Me3 SiCH2 )2 InAs(SiMe3 )2 In- Dehalosilylation144 6:2:6 ratio, [Li(THF)4 ]2 [(MesInCl)6 (InCl)2 [(AsBu)(t-Bu)]6 ]
(CH2 SiMe3 )2 Cl is isolated.149
[(Me3 Si)2 AsInMe2 ]2 Dehalosilylation148 An X-ray diffraction study indicates that [Me2 AsInMe2 ]3
(Me3 Si)3 AsIn(Me3 SiCH2 )3 Salt elimination;111 direct111 contains two independent molecules per asymmetric unit
(MesInCl)4 (InCl)2 [As(t-Bu)]4 Salt elimination149 in the solid state,152 one with a planar (AsIn)3 ring while
[Li(THF)4 ]2 (MesInCl)6 (InCl)2 - Salt elimination149
[(AsBu)t-Bu]6
the other is puckered. However, a dynamic 1 H NMR study
(Me3 Si)3 AsIn(CH2 CMe3 )3 Direct150 indicates equivalence of the indium methyls and of the arsenic
(Me3 SiCH2 )2 InAs(SiMe3 )2 - Equilibration151 methyls in solution down to 80 C. [(t-Bu)2 AsInMe2 ]2 65,119
In(CH2 SiMe3 )2 P(SiMe3 )2 is dimeric by X-ray and mass spectral studies and the (AsIn)2
core is planar.
The (AsIn)2 ring is slightly puckered in [(Me3 Si)2 -
organometallic AsIn bonded compounds and indicates their AsInPh2 ]2 ,145 whereas the (PIn)2 core in [(Me3 Si)2 PInPh2 ]2
method of synthesis. [Me2 AsInMe2 ]3 ,62 [Ph2 AsInMe2 ]2 ,70 is planar in the solid state. Both the (AsIn)2 ring of
and [(t-Bu)2 AsInMe2 ]2 65 were prepared by reacting the [(Me3 Si)2 AsIn(CH2 SiMe3 )2 ]2 and the InAsInCl ring of
respective secondary arsine with Me3 In. Four-membered (Me3 SiCH2 )2 InAs(SiMe3 )2 In(CH2 SiMe3 )2 Cl are planar by
arsinoindanes with arsenic and mixed AsCl bridging have single-crystal X-ray diffraction studies.144
been synthesized by the salt elimination and dehalosilylation
methods.65,128,144,145 Dehalosilylation results in the formation
of [Ph2 InAs(SiMe3 )2 ]2 from the room-temperature reaction
of Ph2 InCl and As(SiMe3 )3 (equation 45).145
6 ORGANOARSENIC COMPOUNDS CONTAINING
AsGROUP 14 BONDS
2Ph2 InCl + 2As(SiMe3 )3 [Ph2 InAs(SiMe3 )2 ]2 + 2Me3 SiCl
(45)
AsGa, AsGe, and AsSn bonded compounds and transition- Pyramidal geometry at arsenic has been inferred in
metal156 complexes. The reaction of BF3 with Me3 SiAsMe2 (Me3 Sn)3 As from vibrational data, in comparison with planar
at 50 C gives a quantitative yield of (Me2 As)2 BF and geometry at N in (Me3 Sn)3 N.5,11 Because the stannylarsines
Me3 SiF. With MeI, cleavage of the SiAs bond occurs with a are not sensitive toward hydrolysis, they can be prepared
dehalosilylation reaction that gives alkylation on the arsenic in aqueous oxygen-free solution. In the presence of oxygen,
(equation 50). Hydrolysis produces the arsine and silyl ether they are oxidized to the stannylarsinates, R3 SnOAs(O)R2 .
(equation 51), and SiCl4 cleaves the AsSi bond to give a Methyl iodide cleaves the SnAs bond and gives the respective
Cl3 Si derivative (equation 52). Me3 SiAsMe2 has been used for tin iodide and arsonium iodide. Phenyl azide reacts with
fluorine substitution with an AsMe2 group in polyfluoroarenes the mono- and bisstannylarsines to give the respective tin-
and C5 NF5 .157 substituted aminoiminoarsines (equation 62).
Me3 SiAsMe2 + MeI Me3 As + Me3 SiI (50) Ph3 SnAsPh2 + 2PhN3 Ph3 Sn(NPh)As(=NPh)Ph2 + 2N2 (62)
2Me3 SiAsMe2 + H2 O 2Me2 AsH + (Me3 Si)2 O (51)
Me3 SiAsMe2 + SiCl4 Me2 AsSiCl3 + Me3 SiCl (52) 6.4 AsPb Bonded Compounds
The importance of the silylarsines in the synthesis The few known plumbylarsines have been prepared by the
of arsinoalanes and arsinogallanes has been discussed reaction of the organolead halide with the sodium arsenide in
in Section 5. Their use in synthesizing germyl- and liquid ammonia (equation 63).61
stannylarsines is discussed below.
Ph3 PbCl + NaAsPh2 Ph3 PbAsPh2 + NaCl (63)
reaction when the reactant aminoarsine is mixed neat with the to the formation of cyclic or cage compounds that contain an
desired secondary amine in the exact mole ratio for complete AsN bonded core. The bulkiness of the amine substituent
substitution.165 Transamination becomes less effective as the and reaction stoichiometry determine the nature of the cyclic
steric bulkiness of the amine increases. or cage AsN core. For example, reaction of PhNH2 with
Although both aminolysis and salt elimination reactions AsI3 in a 4:1 mol ratio yields As(HNPh)2 I, which decomposes
can be used to give cyclic aminoarsines, aminolysis with with cyclization to an AsN tetrameric core, [IAsNPh]4
a diamine is the best route (equation 69). Transamination (equations 80 and 81).
of As(NMe2 )3 with a symmetrical hydrazine provides a
synthetic route to a caged species (equation 70). Cleavage 4PhNH2 + AsI3 As(HNPh)2 I + 2[PhNH3 ]+ I (80)
of the heterocyclic NPN bond with AsCl3 yields the cage 4As(HNPh)2 I [IAsNPh]4 + 4PhNH2 (81)
compound As[MeNCH2 CH2 NMe]3 As (equation 71).
numerous other organoarsenic compounds that are otherwise Heating Ph2 AsN3 , which is synthesized from the reaction
difficult to prepare (see Section 2).162,163 of Ph2 AsCl with lithium azide, leads to the tetrameric arsazene
[Ph2 AsN]4 (equation 93). Pyrolysis of the dialkylarsine
MeAs(NMe2 )2 + 4HCl MeAsCl2 + 2[Me2 NH2 ]+ Cl (86) azides does not yield an AsN bonded product. The
2Et2 AsNMe2 + H2 O (Et2 As)2 O + 2Me2 NH (87) tetrameric [Ph2 AsN]4 can also be obtained by the reaction
of Ph2 AsCl3 with NH4 Cl in liquid ammonia (equation 94)
Me2 AsNEt2 + EtOH Me2 AsOEt + Et2 NH (88)
or from the conversion of the trimeric [Ph2 AsN]3 that
2As(NMe2 )3 + 3EtCH2 CHO occurs in hot acetonitrile (equation 95). This trimer forms
As2 O3 + 3Me2 NH + 3Me2 NCH=CHEt (89) from the high-pressure, room-temperature ammonolysis of
Ph2 AsCl3 (equation 96), or the chloramination of Ph2 AsCl
Several studies have been conducted on the reactivity in the presence of NH3 (equation 97). Treating As(OMe)5
of diborane, BH3 THF, -Me2 NB2 H5 , and aluminum alkyls with ammonia in methanol gives NH4 [As(OMe)6 ], which
toward aminoarsines.19,20,63,82,84,168,169 These reactions have loses methanol in vacuo to give material that is primarily
been followed using multinuclear NMR to establish bonding [AsN(OMe)2 ]3 , but also contains the tetramer, pentamer, and
site in the adducts and deduce the reaction pathway to the hexamer.
thermodynamic stable products. With the series Me2 AsNR2
(R = Me, Et, Pr, i-Pr), the BH3 binding site is dependent 4Ph2 AsN3 [Ph2 AsN]4 + 4N2 (93)
upon the bulkiness of the R group. Increasing bulkiness favors 4Ph2 AsCl3 + 4NH4 Cl [Ph2 AsN]4 + 16HCl (94)
binding on the arsenic atom. Whereas, at low temperature, 4[Ph2 AsN]3 3[Ph2 AsN]4 (95)
exclusive NB binding occurs when R = Me, both AsB and
3Ph2 AsCl + 6NH3 [Ph2 AsN]3 + 3NH4 Cl + 3H2 (96)
NB binding is observed with Et and Pr derivatives, and only
AsB binding arises when R = i-Pr (equation 90). 3Ph2 AsCl + 6NH3 + 3NH2 Cl
2Me2 AsNEt2 + 2BH3 THF
[Ph2 As(NH2 )=NAs(NH2 )Ph2 ]Cl [Ph2 AsN]3 + 6NH4 Cl(97)
Me2 As(BH3 )NEt2 + Me2 AsN(BH3 )Et2 + 2THF (90)
Dehydrochlorination of the aminoarsonium chloride
[Ph3 AsNH2 ]Cl with sodium amide in liquid ammo-
With increasing temperature the AsB adducts convert to
nia produces the triphenylarsinimine Ph3 As=NH. (p-
the NB adduct, except for the i-Pr compound, which is stable
MeC6 H4 )3 As reacts with S4 N4 at 50 C to produce (p-
at room temperature, and decomposition leads to the formation
MeC6 H4 )3 As=NS3 N3 .173 Treating Ph3 As with the azide
of Me2 AsAsMe2 , Me2 AsH, [R2 NBH2 ]2 , and R2 NHBH3 . The
C6 F5 N3 gives, upon heating, the arsinimine Ph3 As=NC6 F5 .
results from the aluminum alkyl reactions have been used to
Ph3 As=NSO2 R species have been prepared from the reaction
develop new syntheses to tertiary arsines (see Section 2).
of Ph3 As with PhI=NSO2 R.174 Also, triphenylarsine oxide
Me3n As(NMe2 )n reacts with R2 PPR2 (R = Me, Et, Ph)
reacts with isocyanates to produce triphenylarsinimines.175
to give the respective aminophosphine and Me2 AsPR2 ,
(o-tolyl)3 B=NCOCCl3 transfers the nitrenoid group to Ph3 As
which further reacts to give Me2 AsAsMe2 .170 With (MeP)5
to yield Ph3 As=NOCCl3 .176 The arsinimines hydrolyze
the reaction yields MeP(NMe2 )2 , Me2 AsAsMe2 , (MeAs)5 ,
with addition of water across the As=N bond to give
and elemental arsenic. Aminoarsines also react with
R3 As(OH)N(H)R . Methylation of the nitrogen atom occurs in
diarsines to generate unsymmetric diarsines, which undergo
the reaction with MeI to yield an arsonium salt (equation 98).
symmetrization.171 The unsymmetric diarsines are also formed
The reaction between Ph3 AsCl2 and (Me3 Si)3 N produces
from the reaction of aminoarsines with secondary arsines,
[Ph3 AsNAsPh3 ]+ Cl (equation 99),177 which can also be
R2 AsH,172 while cyclopolyarsines form in the reactions with
prepared by heating [Ph3 AsNH2 ]Cl. A PNAs bonded ana-
primary arsines, RAsH2 .56
log, [Me3 PNAsMe3 ]+ I , is synthesized by methylating the
product of the reaction between Me3 PNLi and Me2 AsCl
7.1.2 Tetracoordinate Arsenic (equations 100 and 101).
Typical tetracoordinate arsenic compounds that contain R3 As=NSiMe3 + MeI [R3 AsN(Me)SiMe3 ]I (98)
an AsN bond are the aminoarsonium salts, the arsazenes, 2Ph3 AsCl2 + (Me3 Si)3 N +
[Ph3 AsNAsPh3 ] Cl + 3Me3 SiCl (99)
and the arsinimines.4,7,11,12,31,162 The aminoarsonium chlorides
Me3 PNLi + Me2 AsCl Me3 P=NAsMe2 + LiCl (100)
are synthesized by the reaction of tertiary arsines with the
following chloramines: NH2 Cl, MeN(H)Cl, and Me2 NCl Me3 P=NAsMe2 + MeI [Me3 PNAsMe3 ]+ I (101)
(equations 91 and 92).30,31
An X-ray study of (Ph2 AsN)3 has shown that the six-
Et3 As + NH2 Cl [Et3 AsNH2 ]Cl (91) membered ring is slightly puckered with all AsN distances
Pr3 As + Me2 NCl [Pr3 AsNMe2 ]Cl (92) equal. The ring in the phosphorus analog (Ph2 PN)3 is more
14 ARSENIC: ORGANOARSENIC CHEMISTRY
nearly planar.11 The corresponding tetramer, (Ph2 AsN)4 , has a Dehalosilylation also provides a pathway to arsinophosphines
nonplanar ring and is isostructural with (Ph2 PN)4 .14 The AsN (equation 104).
distances, in the trimer (1.758 A) and the tetramer (1.73 A),
are shorter than the single bond value (1.87 A). This suggests 2H3 SiPH2 + F3 CAsI2 2H3 SiI + F3 CAs(PH2 )2 (104)
some degree of -bonding in the oligomers. Other AsN ring
systems have been reviewed.14 The AsN bond distance in The direct reaction between a tertiary phosphine and a
[Ph3 AsNAsPh3 ]+ Cl has been reported as 1.749 A.177 haloarsine yields an arsinophosphonium salt (equation 105).
Variable-temperature NMR has been employed to study
barriers of rotation in AsN bonded compounds.12,37 Both Me2 AsCl + Et3 P [Me2 AsPEt3 ]Cl (105)
13
C and 1 H NMR spectral data have been published for
a homologous series of tertiary arsines, aminoarsines, and The introduction of sterically demanding substituents
arsonium and aminoarsonium salts.42 In addition, individual on P and As coupled with particular synthetic strate-
1
H and 13 C NMR spectral data are available for individual gies has blocked oligomerization and permitted the
aminoarsines.20,30,84,165,169,171 preparation of P=As bond containing species, that is
arsaphosphenes.185 For example, base-promoted (DBU)
7.1.3 Pentacoordinate Arsenic condensation has provided a synthetic pathway to (2,4,6-
t-Bu3 C6 H2 )P=AsCH(SiMe3 )2 from (2,4,6-t-Bu3 C6 H2 )PH2
The general synthesis route to pentacoordinate arsenic and (Me3 Si)2 C(H)AsCl2 .186 Similarly the analogous (2,4,6-
compounds that contain an AsN bond is the aminolysis t-Bu3 C6 H2 )As=PCH(SiMe3 )2 has been synthesized, in
of a pentacoordinate oxyarsorane with a primary amine addition to MesP=AsCH(SiMe3 )2 , MesAs=PCH(SiMe3 )2 ,
(equation 102).13,31,45 With PhNH2 in excess, polymeric and MesAs=PCp . MesP=AsC6 H3 -2,6-Trip2 (Trip = 2,4,6-
pentacoordinate arsenic species are obtained. The chlo- i-Pr3 ) forms in the direct reaction of MesPLi2 and
rination of (CF3 )2 AsN(SiMe3 )2 in a 1:1 mol ratio gives 2,6-Trip2 H3 C6 AsCl2 .187 A t-BuLi reductive coupling reac-
(CF3 )2 As(Cl)2 N(SiMe3 )2 , while an excess of Cl2 produces tion between (Me3 Si)3 CAsCl2 and (Me3 Si)3 CPCl2 gives
[(CF3 )2 As(Cl)NSiMe3 ]2 via a dehalosilylation reaction. Sev- (Me3 Si)3 CAs=PC(SiMe3 )3 . Two pathways have been devel-
eral other pentacoordinate arsenic species have been prepared oped to (2,4,6-t-Bu3 C6 H2 )P=AsCp that use either dehy-
by specialized routes, which have been reviewed.31,45 drochlorination or dehalosilylation (equations 106 and
107).179
2(MeO)5 As + 4H2 NPr [(MeO)2 (PrNH)AsNPr]2 + 6MeOH
(102) Cp AsCl2 + (2, 4, 6-t-Bu3 C6 H2 )PHLi + DBU
(2, 4, 6-t-Bu3 C6 H2 )P=AsCp + LiCl + DBUHCl (106)
Cp AsCl2 + (2, 4, 6-t-Bu3 C6 H2 )P(SiMe3 )Li
7.2 AsP Bonded Compounds
(2, 4, 6-t-Bu3 C6 H2 )P=AsCp + LiCl + Me3 SiCl (107)
Both AsP and As=P bonded compounds have been
prepared.12,31,178187 The earliest demonstrated routes to All the PAs and P=As bonded compounds are sensi-
arsinophosphines were the exchange reactions involving tive to hydrolysis and to oxidation by air. The reaction
(CF3 P)4 and Me2 AsAsMe2 to give Me2 AsP(CF3 )AsMe2 of Cp As=PMes with diazomethane adds a CH2 group
and Me2 AsH and (CF3 )2 PP(CF3 )2 to yield (CF3 )2 PAsMe2 . across the double bond and yields the three-membered het-
A quantitative yield of (CF3 )2 PAsMe2 also results from erocyclic phosphaarsirane Cp AsCH2 PMes.184 Sulfur and
the reaction of (CF3 )2 PP(CF3 )2 with Me2 AsAsMe2 .188 An selenium add across the double bond to form three-
analogous exchange reaction that includes (CF3 )2 PP(CF3 )2 membered heterocycles.186 Dimerization of Cp As=PCp
and (CF3 )2 AsAs(CF3 )2 gives an equilibrium statistical produces two isomeric diphosphadiarsetanes, one contain-
distribution of reactants and (CF3 )2 PAs(CF3 )2 . An equilibrium ing the PPAsAs and the other the PAsPAs core.
distribution of reactants and products, with Keq = 0.37 in Photolysis of Cp As=PMes, Cp P=AsMes, and (2,4,6-
benzene at 30 C, occurs when Ph2 PPPh2 and Ph2 AsAsPh2 t-Bu3 C6 H2 )P=AsCp yields the diarsadiphosphacyclo-
are mixed (equation 103). butanes.183,186 Metal complexes of several of the P=As
compounds have been prepared and characterized.189
Ph2 PPPh2 + Ph2 AsAsPh2
2Ph2 PAsPh2 (103) 31
P NMR chemical shift data have been used extensively
to confirm double bond formation in phosphaarsenes and
The reaction of Me2 AsNMe2 with R2 PPR2 (R = Me, diphosphenes.178,186 The 31 P chemical shift range for these
Et, Ph) gives R2 PNMe2 and R2 PAsMe2 , and the latter compounds is typically from +500 to +700 ppm (85%
reacts further with Me2 AsNMe2 to produce Me2 AsAsMe2 H3 PO4 ). The shifts are among the lowest known in 31 P NMR.
31
and R2 PNMe2 .170 Silane elimination occurs in the reaction P NMR chemical shifts for phosphinoarsines are similar to
of Me3 SiAsMe2 with (CF3 )2 PH to give (CF3 )2 PAsMe2 . those for diphosphines and aminophosphines.170,179,188
ARSENIC: ORGANOARSENIC CHEMISTRY 15
From X-ray crystallographic studies, the observed distances Very few asymmetric substituted diarsines are known.
for P=P, P=As, and As=As (see Section 7.3) bonds are Cp (CH3 )AsAs(CH3 )Cp has been prepared in high yield
2.0, 2.1, and 2.2 A respectively.178,181,186 In general, the by reacting MeLi with Cp (Cl)AsAs(Cl)Cp . The latter
compounds adopt a trans configuration and the RE=E R is obtained in high yield from the reductive coupling of
skeleton is planar. Normal PAs and AsAs single bond Cp AsCl2 with cobaltocene in hexane.191
distances are assumed to be 2.34 and 2.44 A respectively. Most of the synthetic pathways to the cyclopolyarsines
However, the PAs and AsAs distances are 2.35 and 2.38 A (RAs)n , where n = 3 6, are analogous to those to the
in [2,4,6-t-Bu3 C6 H2 PAs]2 .183 diarsines. For example, the reduction of arsonic acids, arson-
ous acids, and organodihaloarsines with hypophosphorous
acids has been widely used. Primary arsines can also be oxi-
7.3 AsAs Bonded Compounds dized by aromatic or aliphatic aldehydes, I2 , Cl2 , SO2 Cl2 ,
The AsAs bonded diarsines and cyclopolyarsines have NH2 Cl, and Me2 NCl. The salt elimination reaction has been
been extensively reviewed.47,912,14,54 The first synthesized used in the low-temperature (78 C) synthesis of (t-BuAs)3 ,
organometallic compound was Me2 AsAsMe2 , which was which converts to (t-BuAs)4 at room temperature (equa-
prepared by heating As2 O3 with KC2 H3 O2 . This compound tions 116 and 117). The methyl and ethyl pentamer derivatives
and other symmetric or unsymmetric diarsines can be readily have been prepared in good yields by the reaction of the
obtained by the reduction of the corresponding arsinic primary arsines with dibenzylmercury.
acid, RR As(O)OH, or diarsoxane, RR AsOAsRR , with
t-BuAs(K)As(K)-t-Bu + t-BuAsCl2 (t-BuAs)3 + 2KCl (116)
hypophosphorous acid in HCl or HI solution. Reaction of the
diarsoxane or a monohaloarsine with a secondary arsine gives 4(t-BuAs)3 3(t-BuAs)4 (117)
the diarsines (equations 108 and 109). When the substituents
on the haloarsine and the secondary arsine are dissimilar, two Reductive coupling of dihaloarsines with Na and Hg
different symmetric diarsines are formed (equation 110). This provides another pathway to several cyclopolyarsines.
is a consequence of the exchange reactions that readily occur (Me3 SiCH2 As)5 has been prepared from the reduction of
in mixtures of AsAs bonded species. Me3 SiCH2 AsCl2 with Mg turnings.49 Using Mg, Ca, Zn, Li,
or CoCp2 in THF as the reducing agents toward t-BuAsI2
(Ph2 As)2 O + 2Ph2 AsH 2Ph2 AsAsPh2 + H2 O (108) promotes reductive coupling and gives high yields of (t-
Me2 AsCl + Me2 AsH Me2 AsAsMe2 + HCl (109) BuAs)4 . With CoCp2 in a 1:1 mol ratio in n-pentane, the
2Ph(CF3 )AsCl + 2(CF3 )2 AsH reduced species is (t-BuAsI)2 .192
When primary arsines are reacted with (MeAs)5 , the
Ph(CF3 )AsAs(CF3 )Ph + (CF3 )2 AsAs(CF2 )2 + 2HCl (110)
respective cyclopolyarsine (RAs)n is prepared in high yield
(equation 118).57,58 Also the reaction of primary arsines with
The salt elimination reaction has also been used as a route
aminoarsines56 and diarsines55 generates cyclopolyarsines.
to diarsines. Reductive coupling of a monohaloarsine with Hg
or Zn gives diarsines. Oxidation of Me2 AsH and Ph2 AsH with n
Cl2 , NH2 Cl, or Me2 NCl gives good yields of Me2 AsAsMe2 n RAsH2 + (MeAs)5 n MeAsH2 + (RAs)n (118)
5
and Ph2 AsAsPh2 respectively (equation 111). Ph2 AsAsPh2
can also be prepared from the oxidation of Ph2 AsMgBr with (MeAs)5 is the yellow form of polymethylarsine, (MeAs)n .
I2 , HgCl2 , Ph2 CCl2 , and Ph2 CHBr (equation 112). Reductive An involatile red form and a sublimable purple-black form
coupling occurs in the reaction of Ph2 AsCl with Bu3 P also exist. The interconversion of these forms on heating is
(equation 113). catalyzed by impurities.
The AsAs bond in the di- and cyclopolyarsines is
2Me2 AsH + NH2 Cl Me2 AsAsMe2 + NH4 Cl (111) easily cleaved using RAsH2 , R2 AsH, Me2 AsNR2 , halogens,
2Ph2 AsMgBr + HgCl2 Ph2 AsAsPh2 + 2MgClBr + Hg (112) methyl iodide, alkali metals, oxygen, and unsaturated organic
2Ph2 AsCl + Bu3 P Ph2 AsAsPh2 + Bu3 PCl2 (113) compounds. In some cases, these reactions provide pathways
to arsenic-containing heterocycles. Reaction of the diarsines
Mes2 AsAsMes2 has been prepared from the reaction of with moist air results in oxidation to the corresponding arsinic
Fe[N(SiMe3 )2 ]2 with HAsMes2 .190 Me2 AsAsMe2 can also be acid (equation 119) and with polyarsines to the arsonic acid
obtained from the reaction of Me2 AsH with Me2 AsNMe2 (equation 120).
or Me2 AsNMe2 BH3 (equation 114).59 The polyarsines
2Me2 AsAsMe2 + 3O2 + 2H2 O 4Me2 As(O)OH (119)
(Ph2 As)3 As and (Ph2 As)2 AsPh are obtained by reacting
Ph2 AsI with the respective stannylarsine (equation 115).54 (MeAs)5 + 5O2 + 5H2 O 5MeAs(O)(OH)2 (120)
Me2 AsH + Me2 AsNMe2 Me2 AsAsMe2 + Me2 NH (114) With the halogens, AsAs bonds are cleaved in the diarsine
(Ph3 Sn)2 AsPh + 2Ph2 AsI (Ph2 As)2 AsPh + 2Ph3 SnI (115) to produce the monohaloarsine and in the cyclopolyarsine
16 ARSENIC: ORGANOARSENIC CHEMISTRY
to give the dihaloarsine. Sulfur and selenium react via an 2.458 A with the phenyl groups in a staggered conformation.
insertion reaction (equation 121). The reactions of primary and Mes2 AsAsMes2 possesses C2 symmetry with the AsAs
secondary arsines toward di- and cyclopolyarsines have been distance being 2.472 A.190 (C6 F5 )4 As2 is rotated 16.5 from
discussed in Section 3. Aminoarsines cleave the AsAs bond a perfect trans conformation, while (Me3 Si)4 As2 deviates
in diarsines to yield unsymmetric diarsines, which undergo significantly (54.3 ) from a trans arrangement. In these two
symmetrization (equations 122 and 123).171 diarsines, the AsAs bond distances are 2.479 and 2.458 A,
respectively.34 Dynamic NMR spectroscopy has been used to
15Se8 + 24(MeAs)5 40(MeAsSe)3 (121) study inversion processes of diarsines.15
Me2 AsNMe2 + Et2 AsAsEt2 Me2 AsAsEt2 + Et2 AsNMe2 (122) Several X-ray diffraction studies of cyclopolyarsines,
2Me2 AsAsEt2 Me2 AsAsMe2 + Et2 AsAsEt2 (123)
(MeAs)5 ,7,11,15 (CF3 As)4 , (t-BuAs)4 , (Me3 SiCH2 As)5 ,49 and
(PhAs)6 , have been reported.14 (MeAs)5 has a puckered five-
membered ring of arsenic atoms with a mean AsAs distance
By analogy with the phosphaarsenes, the bulky (Me3 Si)3 C of 2.428 A. In contrast, the purple-black form of (MeAs)n has
and Mes moities on arsenic facilitate the isolation of an unusual ladder-like structure in which the horizontal AsAs
As=As species.185,193 During the reductive coupling of distances are typical of single AsAs bonds (2.4 A), but the
(Me3 Si)3 CPCl2 and (Me3 Si)3 CAsCl2 with t-BuLi, the vertical distances are very long (2.9 A).11,197 In (CF3 As)4 , the
diarsene (Me3 Si)3 CAs=AsC(SiMe3 )3 is formed.186 This four-membered ring is nonplanar with an AsAs bond distance
diarsene is also produced by the reductive coupling of 2.454 A. (Me3 SiCH2 As)5 has a solid-state conformation
of (Me3 Si)3 CAsCl2 with t-BuLi and in the reaction similar to (MeAs)5 .49 In the hexamer (PhAs)6 , the ring is
of (Me3 Si)3 CAsCl2 with Na2 Cr2 (CO)10 . The bulky Mes puckered (chair) and the average AsAs distance is 2.459 A.
substituent also prevents oligomerization and permits isolation The 1 H NMR spectrum of (MeAs)5 consists of three single
of MesAs=AsMes (equation 124). The latter is also resonances with relative intensities of 2:2:1.11 However, in the
formed from the reaction of Cp (CO)2 FeP(SiMe3 )2 and solid state, all methyl groups are nonequivalent.15 Variable-
MesAsCl2 . The base-catalyzed condensation reaction yields
temperature NMR studies on this and other cyclopolyarsines
an unsymmetric diarsene (equation 125).
have been performed.14
From these studies, two motional processes have been
2MesAsCl2 + 2Mg MesAs=AsMes + 2MgCl2 (124)
postulated, a low-energy pseudorotational motion and a
(Me3 Si)2 CHAsCl2 + H2 AsMes + 2DBU higher-energy arsenic atom inversion process. Detailed
(Me2 Si)2 CHAs=AsMes + 2HClDBU (125) equilibrium studies have been conducted involving ring, chain,
and oligomeric forms of these species.11,15,197
2,6-(Mes)2 H3 C6 As=AsC6 H3 2,6-(Mes)2 and 2,4,6-(i-
Pr)3 H2 C6 As=AsC6 H2 -2,4,6-(i-Pr)3 were synthesized by
reductive coupling with Mg of the corresponding
dihaloarsines.194 A salt elimination reaction involving 8 ORGANOARSENIC COMPOUNDS CONTAINING
2,4,6-(t-Bu)3 C6 H2 AsF2 and LiAsC6 H2 -2,4,6-(t-Bu)3 gives AsO BONDS
excellent yields of 2,4,6-(t-Bu)3 C6 H2 As=AsC6 H2 -2,4,6-(t-
Bu)3 .195 Sulfur adds across the diarsene double bond The synthesis and reactivity of organoarsenic com-
to produce the three-membered heterocyclic thiadiarsir- pounds that contain AsO bonds has been extensively
anes MesAs(S)AsMes and (Me3 Si)3 CAs(S)AsC(SiMe3 )3 . reviewed.47,911 Because of space limitations, the extensive
Diazomethane reacts with MesAs=AsMes to give the three- chemistry associated with AsO bonded systems cannot be
membered heterocyclic diarsirane MesAs(CH2 )AsMes. covered. Instead, the highlights of the chemistry will be pre-
The transition-metal chemistry and nature of the complexes sented here and the reader is referred to the reviews for the
formed with AsAs bonded compounds has been reviewed.196 vast quantity of more detailed information. These highlights
The reader is referred to this comprehensive review for an have been grouped according to the more common classes of
overview of the nature of complexes that contain chains of AsO bonded compounds that serve as precursors to many of
coordinated RAs units, heterocyclic Aschalcogen rings, the compounds discussed in earlier sections of this review.
and unsubstituted arsenic atoms and for references to the
primary literature. The limited transition-metal chemistry of
the phosphaarsenes and diarsenes is also reviewed.186 8.1 Arsonous Acids, Anhydrides, and Esters
Few diarsines have been structurally characterized. From
X-ray data, crystalline tetramethyldiarsine exists in the trans These AsO bonded species are related by the fact that they
form. However, Raman spectra of the liquid and electron contain arsenic in the +3 oxidation state and have one organo
diffraction and photoelectron spectroscopy data of the vapor substituent bonded to the arsenic. The general formulas are as
indicate both gauche and trans forms present.79 In the follows: arsonous acids, RAs(OH)2 ; arsonous acid anhydrides,
solid state, Ph2 AsAsPh2 has an AsAs bond length of RAsO; arsonous acid esters, RAs(OR )2 .
ARSENIC: ORGANOARSENIC CHEMISTRY 17
The arsonous acids or acid anhydrides are obtained in the reaction of aluminum trialkyls or Grignard reagents with
hydrolysis of dihalo-, dialkoxy-dicyano-, and bisaminoarsines. As2 O3 (equation 133). (Me2 As)2 O is also obtained, in addition
The nature of R usually determines whether the acid or the to other products, upon heating a mixture of As2 O3 and
anhydride is formed. When R is aliphatic or aromatic, with potassium acetate.
an unsubstituted ring, the anhydride is the primary product
(equation 126). 2Me2 AsNMe2 + H2 O (Me2 As)2 O + 2Me2 NH (132)
(Me3 Al)2 + As2 O3 (Me2 As)2 O + 2MeAlO (133)
1
MeAs(NMe2 )2 + H2 O (MeAsO)n + 2Me2 NH (126)
n
By analogy with the arsonous acid esters, the arsinous acid
If R is aromatic with electron-withdrawing substituents, esters form in the reaction of monohaloarsines with sodium
the acid is the major product. Because the anhydride is alkoxides (equation 134). The alcoholysis of the diarsoxanes
thought to be in equilibrium with the acid in solution, the in the presence of copper sulfate also produces arsonous acid
separation conditions can determine whether the acid or esters.
anhydride is obtained. Because many dihaloarsines dissolve
in water without appreciable hydrolysis, the addition of base Et2 AsCl + NaOPh Et2 AsOPh + NaCl (134)
is required to form the acid salt. Reduction of an arsonic
acid, RAsO(OH)2 , in hydrochloric acid with SO2 and I as
a catalyst gives the anhydride (equation 127). The anhydride 8.3 Arsonic and Arsinic Acids
is also produced during the oxidation of cyclopolyarsines and
These AsO bonded species are related by the fact that
primary arsines in the absence of water (equation 128).
they contain arsenic in the +5 oxidation state. The arsonic
acids, RAsO(OH)2 , have one organo substituent bonded to
1
MeAsO(OH)2 + SO2 (MeAsO)n + H2 SO4 (127) the arsenic, while the arsinic acids, R2 As(O)OH, have two.
n
n n The most common preparative methods involve isolating the
(MeAs)5 + O2 (MeAsO)n (128) sodium or potassium salt.
5 2
Historically, the Meyer reaction, which consists of
The arsonous esters are easily synthesized by the reaction alkylating metal arsenites with alkyl halides, is the most
of the dihaloarsines with alcohols or alkoxides. With alcohols, widely used preparative method for alkylarsonic acid salts
CaCl2 must be present because the esters are very sensitive (equation 135). Subsequent alkylation of the alkylarsonic
toward hydrolysis, which leads to the reformation of the acid salt gives the alkylarsinic acid salt (equation 136).
anhydride (equation 129). The reaction of an alcohol with a Excellent yields of alkylarylarsinic acid salts are obtained
bisaminoarsine leads to an arsonous ester (equation 130), as upon alkylating an arylarsonic acid salt. Aryl halides do not
does the alcoholysis of the anhydride. Reaction of diols with give satisfactory yields of the arylarsonic acid salts.
bis(dimethylamino)alkylarsines leads to esters of macrocyclic
arsinous acid.198,199 EtI + Na3 AsO3 EtAs(O)(ONa)2 + NaI (135)
EtI + EtAs(O)(ONa)2 Et2 As(O)(ONa) + NaI (136)
EtAsCl2 + 2NaOMe EtAs(OMe)2 + 2NaCl (129)
MeAs(NMe2 )2 + 2PhOH MeAs(OPh)2 + 2Me2 NH (130) The Bart reaction, which consists of reacting Na3 AsO3
(sodium arsenite) with aromatic diazonium salts in buffered
alkaline solution (pH = 8.8 9.2), provides an established
8.2 Arsinous Acids, Anhydrides, and Esters
route to the arylarsonic acids (equation 137). A useful variation
These AsO bonded species are related by the fact that they consists of reacting the diazonium fluoroborates with AsCl3
contain arsenic in the +3 oxidation state and have two organo in a nonaqueous solvent and then hydrolyzing the products to
substituents bonded to the arsenic. The general formulas are produce a mixture of arylarsonic and diarylarsinic acids.
as follows: arsinous acids, R2 AsOH; arsinous acid anhydrides Anhydrous conditions favor the arsonic acid, while the
or diarsoxanes, (R2 As)2 O; arsinous acid esters, R2 AsOR . presence of water favors the arsinic acid.
The arsinous acids and diarsoxanes can be prepared by the
hydrolysis of the monohalo-, amino-, or alkoxyarsines or the RN2 + X + Na3 AsO3 RAsO(ONa)2 + N2 + NaX (137)
base hydrolysis of diarsoxanes (equation 131).
H3 AsO4 arsonates phenyl ethers, phenols, and aromatic
(Ph2 As)2 O + H2 O 2Ph2 AsOH (131) amines. The yields are usually low and arsonation occurs in
the para position (equation 138).
The diarsoxanes are formed in the base hydrolysis of
aminoarsines and monohaloarsines (equation 132) and in the C6 H5 OH + H3 AsO4 p-HOC6 H4 AsO(OH)2 + H2 O (138)
18 ARSENIC: ORGANOARSENIC CHEMISTRY
A useful route to dialkylarsinic acids involves the acid 10. M. Dub, Organometallic Compounds, Methods of Synthesis,
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22 ARSENIC: ORGANOARSENIC CHEMISTRY
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Asymmetric Synthesis by it is often found that reaction mechanisms are more
complicated than initially anticipated. Nonetheless, detailed
Homogeneous Catalysis mechanistic studies are of great value and have increased our
understanding of catalytic asymmetric reactions. They can
also position researchers to develop improved catalysts, and
Patrick J. Walsh even new reactions.
University of Pennsylvania, Philadelphia, PA, USA The past several years have witnessed enormous advances
in the number and variety of reactions that can be catalyzed
Based in part on the article Asymmetric Synthesis by Homogeneous with excellent enantioselectivities (see Enantioselectivity).
Catalysis by Brice Bosnich which appeared in the Encyclopedia of The area has recently been comprehensively reviewed with
Inorganic Chemistry, First Edition.
volumes edited by the team of Jacobsen, Pfaltz, and
Yamamoto1 as well as Ojima.2 These important treatises
1 Introduction 1 are quite detailed and cannot be summarized here. The goal
2 The Traditional Method to Screening Asymmetric of this section is to present some of the most important
Catalysts 2 new approaches to asymmetric catalysis. The basic concepts
3 Nontraditional Approaches to Asymmetric Catalysis 4 necessary to understanding catalytic asymmetric reactions
4 Final Perspective 22 have been succinctly described by Bosnich3 in the first edition
5 Related Articles 22 of Encyclopedia of Inorganic Chemistry and will not be
6 References 22 duplicated here.
While impressive progress has been made in asymmetric
catalysis, it must be emphasized that most catalysts do not
meet the criteria of exhibiting high turnover (see Turnover)
Abbreviations
frequency (TOF) and turnover number (TON), and being
ee = enantiomeric excess; TOF = turnover frequency; high yielding, highly enantioselective, easy to prepare, and
TON = turnover number; HKR = hydrolytic kinetic res- stable to trace impurities such as air and moisture.4 Given the
olution; BINOL = 1, 1 -bi-2-naphthol; BIPHEP = 2, 2 - limitations of most catalysts, there remains significant room
bis(diphenylphosphino)-1,1 -biphenyl; DPEN = 1,2-diphen- for improvement and innovation in this field.
ylethylenediamine; Xyl-BINAP = 2,2 -bis(di(3,5-dimethyl- This summary is designed to introduce chemists with a
phenyl)phosphino)-1,1 -binaphthalene; BINAP = 2, 2 -bis- background in inorganic chemistry to the field of asymmetric
(diphenylphosphino)-1,1 -binaphthalene; DM-DABN = N , catalysis. The skills regularly employed by solution phase
N -dimethyl diaminobinaphthyl; Tol-BINAP = 2, 2 -bis(di(4- inorganic chemists are of great value in this area. The
methylphenyl)phosphino)-1,1 -binaphthalene; MBP-H2 = ability to synthesize, isolate, and characterize highly air
methylene bis(phenol); MBP = methylene bis(phenoxide). or moisture sensitive compounds are important tools to
probe catalyst structure. Experience in performing detailed
kinetic and mechanistic studies are essential to understanding
reaction mechanisms in asymmetric catalysis. Based on
the insight gained through these studies, the likelihood of
developing an improved catalyst is greatly increased. It must
1 INTRODUCTION be borne in mind that although the development of new
catalysts is clearly important, it does not always have the
The field of asymmetric catalysis has moved to the forefront lasting impact and value as mechanistic studies. Catalysts
of organic chemistry, culminating with the award of the 2001 like the titanium tartrate-based system for the asymmetric
Nobel Prize in Chemistry to Knowles, Noyori, and Sharpless. epoxidation of prochiral allylic alcohols developed by
The goal of this tremendous effort continues to be the efficient Sharpless and Katsuki,5,6 which has been the catalyst of choice
generation of enantioenriched organic compounds. It is not for this transformation for almost 25 years, are extremely
surprising, therefore, that the practitioners of this popular rare. Catalysts with greater efficiency, enantioselectivity,
field are overwhelmingly organic chemists, despite the fact substrate scope, and functional group compatibility are
that asymmetric catalysis is a discipline that is dependent constantly being introduced. As a result, todays best catalyst
on the synthesis and evaluation of inorganic catalysts. The is tomorrows dog and may soon to be forgotten. In
chemical community has stressed the importance of generating contrast, mechanistic studies serve as guiding principles on
functionalized chiral products of high enantiomeric excess which future catalysts will be developed. Despite the large
(ee) and less emphasis has been placed on understanding the number of catalysts that have been reported, relatively few
structure and the function of the catalyst. To some degree are understood. Thus, mechanistic investigations of known
this is understandable, because mechanistic investigations are reactions represent an excellent entry into the field of
inherently more difficult than catalyst screening. Furthermore, asymmetric catalysis.
2 ASYMMETRIC SYNTHESIS BY HOMOGENEOUS CATALYSIS
t Bu
t Bu
N O Ph N O Ph
Mn Cl Mn Cl
N O Ph N O Ph
t Bu
t Bu
(a)
+
Et
O Et
R2 R1 Zn
O
t- Bu N
O
N
O Oi -Pr
Ti
N
i- PrO O
N
t- Bu
(b)
O O
O O
N O O N
Co OAc AcO Co
N O O N
O O
O O n
(c) n = 1 3
Figure 1 Structures of some metal salen complexes: (a) epoxidation catalysts, (b) proposed structure in the asymmetric addition of alkyl
groups to alpha ketoesters with a bifunctional catalyst, and (c) oligomeric bifunctional salen catalyst for the hydrolytic catalytic resolution
These transformations provide an indication of how the generation of structurally diverse ligands and com-
different salen and metal combinations have been devel- plexes. In this regard, there are no ligands systems that
oped to optimize enantioselectivities and efficiency diverse are better suited to the traditional approach to asymmet-
reactions. The modular nature of the salen ligand allows ric catalysis.
4 ASYMMETRIC SYNTHESIS BY HOMOGENEOUS CATALYSIS
O (salen)Co(OAc) O HO OH
+ In the catalyst optimization process, a series of chiral
H2O
R R
bidentate ligands or chiral monodentate ligands could be
R
screened. An alternative approach that provides access to a
OH greater number of catalysts involves examination of mixtures
Me Me of two monodentate ligands (L1 and L2 ). If these ligands
O
(salen)MnCl
O are part of a larger set of monodentate ligands (L1 , L2 ,
PhIO L3 ,. . . Lx , Ly ), many catalysts with combinations of
Me Me
ligands can be generated. As shown in Figure 2, combining
O two chiral ligands gives rise to formation of three catalysts,
(salen)Mn+ two homochiral complexes, (Lx )2 Rh and (Ly )2 Rh, and a
S S +
Ph Me PhIO Ph Me heterochiral complex (Lx )(Ly )Rh.
These catalysts are likely to have different stabilities and be
(salen)Mn+ formed in unequal amounts. Both the homochiral complexes
TsN
PhINTs (Lx )2 Rh and (Ly )2 Rh are accessible by combining a chiral
Ar Ar ligand with the rhodium precursor. The heterochiral complex,
however, is new. If the heterochiral complex exhibits greater
O O
(salen)Ti(OiPr) 2 Et activity and enantioselectivity than the homochiral complexes,
O OH
MeO ZnEt2 MeO not only will the resulting combination lead to improved
R R
Table 1 Ratios of homo- and heterochiral complexes determined by 3.2 Screening of Heterochiral (L)(L )Ti Complexes in
31
P NMR the Asymmetric Hetero-Diels-Alder Reactions
(L1 )2 Rh (L1 )(L2 ) Rh (L2 )2 Rh In a study aimed at the development of a highly enan-
L1 /L2 17 78 5 tioselective catalyst for the asymmetric hetero-Diels Alder
L1 /L3 5 91 4 reaction, a series of diols and BINOL derivatives was
L2 /L3 27 54 19 employed (Figure 5, L1 L13). Titanium tetraisopropoxide
was chosen as the metal precursor, because it readily under-
goes alkoxide exchange reactions with alcohols and phenols.
Furthermore, it has been successfully used in many Lewis acid
catalysts, it will indicate that a combinatorial approach to (see Lewis Acids & Bases) catalyzed reactions. A beneficial
catalyst optimization is possible. feature of titanium tetraisopropoxide is that chelating alkox-
A small collection of ligands was examined to evaluate the ide and aryloxide-based ligands and/or ligands with acidic
potential of this approach (Figure 3). hydroxyl groups will favor formation of the chiral titanium
Initially two equivalents of each ligand were combined with complex and liberation of isopropanol. By combining all pos-
Rh(acac)(CH2 =CH2 )2 to determine the 31 P NMR chemical sible combinations of L1 L13, a library of 104 combinations
shifts of the homochiral complexes. Next, 1:1 mixtures can be generated. Each of the ligand combinations above will
of chiral ligands were combined with an equivalent of likely result in a mixture of compounds that is under thermody-
the Rh(acac) (CH2 =CH2 )2 and the ratio of the resultant namic control. It is anticipated that the titanium centers will be
coordinated to either two of the same ligands giving (Lm)2 Ti
complexes determined. As outlined in Table 1, the results of
and (Ln)2 Ti or two different ligands as in (Lm)(Ln)Ti.
these experiments suggest that when L1 , with the smallest
Combination of 1 mol% of each ligand and titanium
cone angle (see Cone Angle), is combined with the sterically
tetraisopropoxide generated the catalyst mixtures that were
bulkier ligands L2 or L3 , the equilibrium lies toward the
screened in the asymmetric hetero-Diels Alder reaction
heterochiral complex. When the sterically demanding ligands
(equation 3). All reactions were conducted in diethyl ether
L2 and L3 are combined, however, the product ratio is closer at rt for 24 h and worked up with trifluoroacetic acid. Pre-
to statistical. liminary screening indicated that combination of ligands with
These ligand combinations were then applied to the substituents at the 3,3 -positions of the BINOL ligands gave
asymmetric addition of aryl boronic acid derivatives to either low yields or enantioselectivities. Combinations involv-
2-cyclohexenone. The results of this study are illustrated ing L4 L7 exhibited high enantioselectivities (77 95%) and
in Figure 4. From this data it can be seen that the good yields (63 100%).
heterochiral ligand combination L1 /L2 exhibited the highest
conversion during the 3 h evaluation period. Furthermore, OMe
the heterochiral complexes L1 /L2 and L1 /L3 are O
significantly more enantioselectivity than the homochiral (1) Ti(OiPr) 4, Ln, Lm O
+
combinations. H R (2) CF3CO2H
Me3SiO O R
Despite the small ligand library employed, this study
clearly indicates the benefit of combining chiral monodentate (3)
ligands in the optimization of catalyst enantioselectivity
and efficiency. As illustrated below, larger libraries of Further screening identified L5/L5/Ti and L5/L6/Ti
bidentate ligands (see Bidentate Ligand) can likewise combinations as the most enantioselective combinations.
be employed. Optimization of L5/L5/Ti and L5/L6/Ti combinations allowed
O O
Rh(acac)(CH2 =CH2)2 (2 mol%)
+ (PhBO)3
Lx * (1 mol%), Ly * (1 mol%)
dioxane, H2O, 60 C, 3h
Ph
Lx */ Ly * % conv. % ee Lx */ Ly * % conv. % ee
L1* / L1* 26 33 L1* /L2* 93 75
L2* / L2* 22 27 L1* /L3* 40 77
L3* / L3* 18 16 L2* /L3* 16 60
Figure 4 The asymmetric conjugate addition of aryl boronic acids to 2-cyclohexenone with ligand combinations L1 L3
6 ASYMMETRIC SYNTHESIS BY HOMOGENEOUS CATALYSIS
Cl
Ph Ph
MeO2C OH OH
O OH OH
OH OH
MeO2C OH O OH
Ph Ph
Cl
L1 L2 L4
L3
Br
OH OH OH
OH OH OH
Br
L5 L6 L7
Br Br Br
OH OH OH
OH OH OH
Br Br
L8 L9 L10
Ph Ph SPh
OH OH OH
OH OH OH
Ph Ph SPh
L11 L12 L13
Figure 5 Ligands L1 L13 for the titanium catalyzed hetero-Diels Alder reaction
the loading of titanium and the ligands to be dropped to Table 2 Comparison of enantioselectivities with L5/L5/Ti and
0.05 mol% under solvent free conditions. In some cases, L5/L6/Ti combinations
loadings could be reduced to 0.005 mol%, which is one of
O
the lowest loadings for Lewis acid catalysts known that gave
OMe O (1) Ti(OiPr) 4, 2L5
>95% ee. X OR
X
Selected results employing 0.05 mol% loading of each H Ti(OiPr) 4, L5, L6
+ O
ligand and titanium tetraisopropoxide are illustrated in (2) CF3CO2H
Me3SiO
Table 2. It is noteworthy that the enantioselectivities obtained
with the L5/L6/Ti combination are 0.1 20% higher than the Substrate ee (%) 2L5/Ti ee (%) L5/L6/Ti ee
L5/L5/Ti combination. These results indicate that the most
X=H 99.3 99.4 0.1
enantioselective catalyst contains both ligands. X = 4-OMe 90.8 98.0 7.2
This series of experiments clearly demonstrates the X = 3-OMe 96.6 99.8 3.2
advantage of screening combinations of ligands. The X = 2-OMe 75.1 95.1 20.0
ASYMMETRIC SYNTHESIS BY HOMOGENEOUS CATALYSIS 7
BIPHEP
Ph2
PPh2 PPh2 P
MLn
PPh2 PPh2 P
Ph2
NUPHOS
R R
Ph2
R PPh2 R PPh2 P
MLn
R PPh2 R PPh2 P
Ph2
R R
cyclo -NUPHOS
R R R
Ph2
PPh2 PPh2 P
MLn
PPh2 PPh2 P
Ph2
R R R
Figure 6 Structures of the normally unresolvable ligands BIPHEN, NUPHOS, and cyclo-NUPHOS and their complexes
disadvantage is that use of mixed ligand combinations can resolve. The metallocycle formed on binding to a substi-
lead to the formation of multiple catalysts under the reaction tutionally inert metal significantly increases the barrier to
conditions. In this case, the situation is further complicated racemization.
by the propensity of titanium complexes to aggregate.29 When rac-(BIPHEP)PtCl2 was treated with Na2 [(S)-
Mechanistic studies on a system containing multiple catalysts (BINOLate)], a kinetic 1:1 ratio of the (BINOLate)Pt(BIPHEP)
would be extremely difficult, because the most abundant diastereomers was isolated. Heating this mixture to 92 122 C
complex may not be the most active. resulted in equilibration of the mixture to form a 95:5
ratio with the (S,S)-diastereomer being thermodynami-
cally favored (equation 4). Interconversion of the diastere-
3.3 Asymmetric Catalysis with Normally Unresolvable
omers likely proceeds by dissociation of a phosphorus
Ligands
from platinum, rotation, and recoordination. The minor
Basic coordination chemistry serves as one of the underly- (R,S)-diastereomer was isolated cleanly by fractional
ing principles in the design, development, and understanding precipitation.31
asymmetric catalysts. By taking advantage of strong, kineti- Two routes were developed to eliminate the BINOLate
cally stable metal-ligand bonds, new enantioenriched catalysts ligand from the platinum (Figure 7). Reaction of the [(R)-
have been prepared that contain ligands that cannot be BIPHEP]Pt[(S)-BINOLate] with hydrochloric acid gave
resolved at room temperature. With proper choice of the [(R)-BIPHEP]PtCl2 . The dichloride [(R)-BIPHEP]PtCl2 was
metal center, however, the barrier to racemization of the then subject to two equivalents silver triflate to furnish the
metal-ligand assembly is significantly higher than that of the Lewis acidic triflate [(R)-BIPHEP]Pt(OTf )2 . Alternatively,
free ligand. [(R)-BIPHEP]Pt[(S)-BINOLate] was converted directly to
One class of ligands that racemizes readily at room the triflate [(R)-BIPHEP]Pt(OTf )2 by exposure to triflic
temperature is based on atropisomeric bidentate phos- acid.
phines such as BIPHEP, NUPHOS, and cyclo-NUPHOS The stereochemical stability of the resolved (BIPHEP)Pt
(Figure 6). For example, the barrier to racemization of derivatives was next examined. The possibility of racemiza-
BIPHEP is 22 kcal mol1 ,30 making it very difficult to tion of the [(R)-BIPHEP]Pt(OTf )2 was addressed by treatment
8 ASYMMETRIC SYNTHESIS BY HOMOGENEOUS CATALYSIS
Ph2
P Cl
Pt
HCl
Ph2 P Cl
Ph2
P O
Pt
2AgOTf
P O
Ph2 HOTf
Ph2
(R,S ) P OTf
Pt
P OTf
Ph2
Pt 2 OTf
P N Ph
Ph2 H2
Ph2
P Cl dr > 98:2
rac- Pt (5)
Na2[(S)-(BINOLate)]
P Cl
Ph2
The stability of (BIPHEP)PtX2 compounds with respect
Ph2 to racemization over several hours at room tempera-
P O ture suggested that these compounds could be employed
Pt as catalysts at room temperature or below. To explore
P O this possibility, [BIPHEP]Pt(OTf )2 was employed in the
Ph2 asymmetric Diels Alder reaction as illustrated in equa-
tion (6). Freshly generated [(R)-BIPHEP]Pt(OTf )2 promoted
(S,S)
the asymmetric Diels Alder reaction forming the prod-
uct in 94:6 endo:exo ratio with the ee of the major
Ph2
diastereomer of 92 94%.31 The enantiomeric excess of the
P O catalyst [(R)-BIPHEP]Pt(OTf )2 was not diminished over
Pt the course of the reaction, as determined by quenching
P O the reaction at >90% conversion with (S,S)-DPEN and
Ph2 subsequent 31 P NMR analysis of the resulting mixture.
The facial selectivity of the asymmetric Diels Alder reac-
(R,S) tion catalyzed by [(R)-BIPHEP]Pt(OTf )2 was the same
(4) as observed with [(R)-BINAP]Pt(OTf )2 with the same
ASYMMETRIC SYNTHESIS BY HOMOGENEOUS CATALYSIS 9
O O Ar Me Ar
Me Me
[(R)-BIPHEP]Pt(OTf) 2
N O + N O N Cl
10 mol%, CH2Cl2 HCl
H
55 C Pd Pd
O (7)
N N Cl
O N Me Me
O Ar Me Ar
O
9294 % ee (R,R)/(R) (R,R)-N2PdCl2
(94:6 endo:exo)
(6) These catalyst precursors, abbreviated N2 PdCl2 in equa-
tion (7), were then employed in the asymmetric Diels Alder
reaction of N -acryloyl oxazolidinone with cyclopentadiene
This, and related systems,33,34 illustrate that bidentate
(equation 8).
phosphine ligands that are not resolvable at room temperature
can adopt stereochemically robust coordination modes when
N2PdCl2
bound to substitutionally inert metals. The importance of
chelating phosphines (see Chelating Ligands) in asymmetric 2AgOTf
catalysis, and the difficulties often encountered in their
O O N2Pd(OTf) 2
resolution, should render this nontraditional strategy useful. +
50 C
N O O
Application of N-chirality in Asymmetric Catalysis.
O N
Another class of ligands that cannot normally be resolvable is O
amines. Free amines with three different substituents are not 20% ee
usually considered chiral, because they undergo rapid lone
(8)
pair inversion at nitrogen with rates on the order of 5 105
s1 at rt.35 Coordination of amines to substitutionally inert
metals freeze nitrogen inversion generating N -chiral ligands Although the catalysts typically gave very high endo/exo
(Figure 8). Dissociation of the amine ligand from the metal, ratios, the enantioselectivities were low. It was found
however, will lead to inversion. that the catalyst did not undergo racemization at nitrogen
In an effort to synthesize enantioenriched diamine under the reaction conditions, indicating that the poor
complexes, prochiral diamines were mixed with K2 [(R)- enantioselectivities reflect the inability of the catalyst to
Me2 -BINOLate] and palladium acetate resulting in the efficiently convey the stereochemical information. This may
formation of the two diastereomers (Figure 9).36 These be due to the similarity in size of the Me and CH2 Ar
diastereomers were both C2 -symmetric and assigned as the substituents on the chiral diamine ligand. Nonetheless,
(R,R)/(R) and (S,S)/(R) configurations based on NMR and this example is illustrates that asymmetric catalysts with
X-ray crystallographic studies. The major diastereomer was only N -chirality are feasible and potentially useful in
separated from the minor by crystallization. asymmetric catalysis.
Treatment of the pure (R,R)/(R) diastereomers with HCl
allowed isolation of the dichlorides, which were determined
3.4 Chiral Poisoning
Ar
Me
Me
N
Ar O
Pd
N N O
Me
Me
Pd(OAc)2 Me Ar Me
N
+
CH2Cl2 /THF (R,R ) /(R ) (major)
Ar
50 C
Me Ar
Me
Me
KO N
O
KO Pd
N O
Me Me
Ar Me
Ar2
Ar2 Cl Cl
P
P Ru(DMF)n
Ru(DMF)n + P
P
Ar2 Cl
Ar Cl
2
Me
H2 N
H2 N
Me
0.5 equiv.
Me
Ar2 Ar 2
Cl H2 Cl
P N P
Ru Ru(DMF)n
P N P
Ar2 Cl H2 Ar 2 Cl
Me
Catalyst precursor
Inactive
Figure 11 Selective binding of the (S)-enantiomer of the precatalyst with the (S)-DM-DABN
Cl
Me
Ar
H2
N
P
Ru N
P H2
Ar2 Ar
Me
Cl
Inhibited catalyst
Steric
interaction
Cl
Me
Ar 2 H2
Ar
P N
P Ru N
H2
Me
Ar
Cl
Not formed
Figure 12 Three-dimensional drawings of the binding of the (S)-enantiomer of the precatalyst with the (S)-DM-DABN. The (R)-enantiomer
of the precatalyst does not bind (S)-DM-DABN owing to a repulsive interaction between two aryl groups on the phosphine and the 3,3 -dimethyl
groups on the diamine
12 ASYMMETRIC SYNTHESIS BY HOMOGENEOUS CATALYSIS
3.5 Addition of Chiral Additives: Asymmetric -complexes, this binding mode is uncommon for ketones.
Activation The distinct characteristics of the CC and CO -bonds
suggest that catalyst selective for these groups will likely
An alternative to the approach chiral poisoning that operate by dissimilar mechanisms. This has indeed been found
also involves use of racemic catalysts has been called to be the case, and mechanistic investigations indicate that the
asymmetric activation.42,43 In this strategy, a racemic catalyst ketone reduction proceeds by an unexpected pathway that does
is reacted with resolved activator that selectively activates one not involve coordination of the substrate to the metal center.
enantiomer of the racemic catalyst precursor. This process Ruthenium catalysts bearing diamine and bidentate phos-
involves binding a resolved ligand to a racemic catalyst, phine ligands, illustrated in equation (9), exhibit high enan-
resulting in the formation of diastereomeric catalysts. There tioselectivity and efficiency in the reduction of ketones.39,4446
are several scenarios in which this mixture of diastereomers Before the application of this catalyst to asymmetric activa-
can give high enantioselectivity. Either both catalysts must tion can be illustrated, important mechanistic information will
give the same enantiomer of the product with high ee, or one of be outlined.
the diastereomeric catalysts must be highly enantioselective
and significantly more active than the other diastereomer.
Cl H2
The advantage of this method over chiral poisoning is that Ar2 N Ph
the resultant catalyst system can exhibit greater activity and P
Ru
enantioselectivity than the enantioenriched precatalyst. P
Ar2 N Ph
O H2 OH
Cl
+ H2
3.5.1 Asymmetric Activation of Racemic Hydrogenation R R
Most examples
Catalysts >95% ee
R1 R1
O O
R2
R2
H H H
H H H H H
H
P N P N P N
Ru Ru Ru
P N P N P N
H H H H
H H
H H H
R1
R2 O
H H
H H H
P N P N P N
Ru Ru Ru
P N P N P N
H H H H
H H
H H H
Figure 13 Proposed mechanism for hydrogenation of ketones with (BINAP)RuH2 (diamine) derivatives
ASYMMETRIC SYNTHESIS BY HOMOGENEOUS CATALYSIS 13
H H H
H H H H
P N P N P N
Ru Ru Ru
P N P N P N
H H H H
H H
H H H
believed to be formation of a weak interaction between the The catalyst composed of the mismatched ligands,
ketone substrate and the catalyst, as shown in Figure 13. From (R)-Xyl-BINAP and (S,S)-DPEN, was much slower and
this hydrogen-bonded intermediate, facile hydrogenation takes furnished the (S)-alcohol with 56% ee (equation 10).
place through a six-membered transition state, resulting Employing racemic Xyl-BINAP and (S,S)-DPEN gave a
in formation of the chiral alcohol and the Ru-amide. 50:50 mixture of diastereomeric ruthenium complexes that
Late transition metal amide complexes of this type are reduced 1 -acetylnaphthone to the (R)-alcohol with excellent
very reactive,4850 and have been characterized in model enantioselectivity (90%).
systems.47
The heterolytic cleavage (see Heterolytic Cleavage) of O OH
RuCl2(phosphine)n
dihydrogen is the turnover-limiting step in the catalytic diamine, KOH
cycle (Figure 14). It likely occurs via initial formation of a + H2
dihydrogen complex (see Hydrogen Bonding & Dihydrogen
Bonding followed by proton abstraction by the amide nitrogen
to give the dihydride complex. Consistent with this hypothesis,
a first-order dependency on the ruthenium catalyst and
the dihydrogen is observed. The reaction is zero order in
Phosphine Diamine % ee
ketone concentration. Additionally, S is on the order of
25 cal molK1 , suggesting a highly ordered transition state. (S)-Tol-BINAP (S,S)-DPEN 40 (R)
(R)-Tol-BINAP (S,S)-DPEN 81 (R)
It is interesting to note that these hydrogenation catalysts (rac)-Tol-BINAP (S,S)-DPEN 80 (R)
are 18 electron species and need not open up a coordination
(11)
site to generate a 16 electron intermediate, as observed with
many alkene hydrogenation catalysts. The bifunctional nature
of these catalysts allows them to access an unconventional Interestingly, when the precatalyst RuCl2 [(S)-Tol-
second-coordination sphere hydrogen transfer mechanism. BINAP][(S,S)-DPEN] (Tol = 4-C6 H4 -Me) was employed in
Activation of the ketone through a hydrogen-bond from the the reduction of 9-acetylanthracene the enantioselectivity was
ligand eludes to the power of such subtle interaction in only 40% (equation 11). In contrast, use of RuCl2 [(R)-
enantioselective catalysis. Tol-BINAP][(S,S)-DPEN] resulted in a reduction of the
This system for the asymmetric hydrogenation of ketones ketone with 81% ee. Employing racemic Tol-BINAP and
has been employed in the asymmetric activation using (S,S)-DPEN gave (R)-alcohol with essentially the same enan-
a racemic BINAP derivative. Combination of RuCl2 [(S)- tioselectivity as the enantioenriched (R)/(S,S)-catalyst.
Xyl-BINAP](dmf )n (Xyl = 3,5-C6 H3 -Me2 ) and (S,S)-DPEN It is noteworthy that in the reduction of 1 -acetylnaphthone
gave the precatalyst RuCl2 [(S)-Xyl-BINAP][(S,S)-DPEN], the catalyst with the (S)/(S,S)-configuration was the fastest
which exhibited 99% enantioselectivity in the reduction of and most enantioselective while in the hydrogenation of 9-
1-acetylnaphthone to the (R)-alcohol (equation 10). acetylanthracene the catalyst with the (R)/(S,S)-configuration
gave the highest enantioselectivity, and exhibited a higher
turnover frequency.
O OH These high enantioselectivities indicate that the diastere-
RuCl2(phosphine)n
diamine, KOH omeric catalysts not only have different enantioselectivities,
+ H2
but must have very different TOFs. Whenever diastereomeric
catalysts are applied together in the same reaction, the prod-
uct ee is governed by the enantioselectivity of each of the
Phosphine Diamine % ee diastereomeric catalysts and their relative rate.5154 This fact
(S)-Xyl-BINAP (S,S)-DPEN >99 (R) complicates reaction optimization. Nonetheless, the results
(R)-Xyl-BINAP (S,S)-DPEN 56 (S) outlined in equation (10) and (11) illustrate how well the
(rac)-Xyl-BINAP (S,S)-DPEN 90 (R) chiral activation strategy can work with the correct combina-
(10) tion of chiral ligands and substrate. It is expected that there
14 ASYMMETRIC SYNTHESIS BY HOMOGENEOUS CATALYSIS
will be a great deal of future activity in asymmetric catalysis a highly enantioselective catalyst that generated 1-phenyl-1-
employing asymmetric activation. propanol of 90% ee at 0 C and 99% ee at 78 C. This catalyst
optimization process illustrates the power of asymmetric acti-
vation to maximize catalyst efficiency and enantioselectivity.
3.6 Asymmetric Activation of Enantioenriched Lewis The asymmetric activation strategy is clearly a useful tech-
Acid Catalysts nique in the optimization of asymmetric catalysis. Racemic
catalysts can by selectively activated with enantioenriched
In the previous example, the asymmetric activation strategy
activators, resulting in the generation of highly enantioselec-
was used to increase the efficiency and enantioselectivity of
tive catalysts. Resolved catalysts can also be activated with
one catalyst in a diastereomeric mixture of catalysts. This
enantioenriched activators, with the potential of increasing
technique can also be applied to resolved asymmetric catalysts.
their efficiency and enantioselectivity. As illustrated above,
An example of this strategy42 involves the zinc catalyzed
this approach can be applied in a combinatorial fashion allow-
asymmetric addition of alkyl groups to aldehydes.55,56
ing generation of a large number of catalysts from a small
Organozinc catalysts are known to promote the asym-
library of ligands.
metric addition of alkyl groups to aldehydes with high
enantioselectivity.57 In the case of catalyst generated from
(R)-3,3-diphenyl BINOL (Ph2 -BINOL) and diethylzinc, how- 3.7 Optimization of Enantioselective Catalysts Using
ever, the asymmetric addition is slow and proceeds in low Achiral and Meso Ligands
enantioselectivity (Figure 15). When the catalyst was pre-
pared in the same fashion, followed by addition of enantiopure The traditional method for the optimization of asymmetric
diimine ligands, new catalysts formed that exhibited increased catalysts involves the synthesis and screening of chiral
efficiencies and enantioselectivities. The levels of enantios- ligands.1 As pointed out in previous sections, the resolution
electivity of the catalysts were then optimized by screening of chiral ligands, or their components, can be demanding
enantiopure diimine ligands. The best catalyst in this study was and time-consuming. In the sections that follow catalyst
derived from (R)-Ph2 -BINOL and the (S,S)-diimine with the enantioselectivity and efficiency are maximized by use
stilbene diamine backbone and 2,4,6-trimethylbenzaldehyde of achiral and meso ligands. The achiral additives can
(Figure 15). Combination of diimine with Ph2 -BINOL gave be divided into three classes: (1) achiral ligands with
Chiral activator
(R )-Ph2-BINOL
ZnEt2
OH
Activated
catalyst
PhCHO + ZnEt2 Ph
up to 99% ee, 78 C
Mes Ph Ar
Ph N N
OH
OH
Ph N N
Mes Ph Ar
(R) -Ph2-BINOL
diamine diamine
config. Ar config. Ar
R,R C6H5 R,R C6H5
R,R 2,6-C6H3-Cl2 R,R 2,6-C6H3-Cl2
R,R 2,4,6-C6H2-Me3 R,R 2,4,6-C6H2-Me3
S,S C6H5 S,S C6H5
S,S 2,6-C6H3-Cl2 S,S 2,6-C6H3-Cl2
S,S 2,4,6-C6H2-Me3 S,S 2,4,6-C6H2-Me3
Figure 15 The asymmetric activation strategy applied to resolved catalysts results in enhanced activity and enantioselectivity
ASYMMETRIC SYNTHESIS BY HOMOGENEOUS CATALYSIS 15
chiral conformations, (2) achiral ligands without chiral several classes of achiral and meso diimines and diamines were
conformation, and (3) ligands that become asymmetric in employed, with only a few representative examples are listed
certain metal geometries. in Tables 4 and 5. Diimines derived from ethylene diamine
were employed and found to lead to enantioselectivities
ranging from 52% ee of the (S)-enantiomer to 87% ee of
3.7.1 Optimization of the Enantioselective Alkylation of the (R)-configuration of the alcohol product (Table 4, entries
Aldehydes Employing Achiral and Meso Ligands 2 5).
In the proceeding section on asymmetric activation, (Ph2 - Imine ligands were also prepared based on the 2,2 -
BINOLate)Zn(diimine) complexes containing two resolved diaminobiphenyl backbone. These ligands will bind to zinc
ligands were employed in the asymmetric alkylation of and adopt chiral binding modes. The barrier to interconversion
aldehydes. In this study, both the Ph2 -BINOL and diimine of such complexes will be significantly higher than the free
could be varied to optimize catalyst enantioselectivity ligands, because ring strain will be incurred in the transition
(Figure 15).55,56 A different approach to catalyst optimization state to atropisomerization of the metallocycle. As depicted
in this system would involve the use of one resolved ligand and in Figure 17, the two enantiomeric conformation of the
one achiral or meso ligand (Figure 16). This strategy could be zinc-bound diaminobiphenyl-based ligands are diastereomeric
termed achiral activation based on its relation to asymmetric in the presence of the (Ph2 -BINOLate)Zn moiety. If the
activation. In the study outlined below, the focus was on using difference in energy of these diastereomers is large, the
achiral or meso ligands with chiral conformations. These equilibrium could lie far to the side of the more stable
ligands are attached to a metal coordinated to a resolved diastereomer resulting in resolution of the diaminobiphenyl
ligand.58,59 Using this strategy, numerous catalysts can be ligand. The chiral conformations of the biphenyl diimine
synthesized from each resolved ligand by combination with ligands extend the chiral environment of the catalyst
an array of achiral and meso ligands. One advantage of (Figure 17). Use of these ligands and (S)-Ph2 -BINOL in
such an optimization process is that many more achiral Figure 16 generated catalysts that exhibited up to 96%
and meso ligand precursors and ligands are commercially enantioselectivity at 45 C (Table 4, entry 7).
available than enantiopure ligands. The greater variation It is interesting to note that catalyst derived from imines
in ligand components allows generation of catalysts with of 2,4,6-trimethylbenzaldehyde were found to result in the
more diverse chiral environments. This, in turn, increases most enantioselective catalysts with resolved, achiral, and
the likelihood of finding a suitable catalyst. Finally, the meso ligands in the asymmetric addition (Figure 15 and
cost of achiral and meso ligands is less than that of related Table 4). This suggests that the placement and orientation
enantiopure materials. of the 2,4,6-trimethylphenyl groups plays a crucial role in the
As proof of principle, and to demonstrate the potential stereoinduction.
utility of the use of achiral and meso ligands in asymmetric In the examination of other nitrogen-based ligands with this
catalysis, the catalyst optimization was performed using catalyst system, it was observed that achiral and meso diamines
a single enantioenriched ligand, (S)-Ph2 -BINOL. In the had a marked impact on catalyst enantioselectivities. The
asymmetric additions to benzaldehyde with ZnEt2 and simple diamines, TMEDA and N,N,N ,N -tetraethylethylene
10 mol% (S)-Ph2 -BINOL, in the absence of additional ligands, diamine were found to exhibit the opposite enantiofacial
(S)-1-phenyl-1-propanol of 44% ee was slowly generated selectivity (Table 5). While TMEDA formed a catalyst
(Table 4, entry 1). After 28 h at 0 C, conversion to the alcohol that gave the (S)-enantiomer of the product in 64%
was only 83%. Subsequent experiments were performed with enantioselectivity (0 C), catalyst based on N,N,N ,N -
achiral or meso ligands and Ph2 -BINOL using 10 mol% tetraethylethylene diamine generated the (R)-enantiomer in
loading of each of these ligands. Three equivalents of up to 72% ee.
diethylzinc were used relative to benzaldehyde. Although Secondary diamine ligands are particularly interesting
because they result in addition of another stereochemical
element to the catalyst. Coordination of secondary diamines
Achiral ligand
to zinc stops nitrogen inversion, creating two new stereogenic
(S )-Ph2-BINOL centers directly attached to the catalyst binding site.60,61 This
ZnEt2 coordination is likely to be reversible, permitting equilibration
of the configuration at nitrogen through a 3-coordinate
OH zinc intermediate. The C2 -symmetric (Ph2 -BINOLate)Zn is
Activated
catalyst expected to bind the diamine in a C2 -symmetric fashion
PhCHO + ZnEt2 Ph
to minimize steric interactions between the diamine and
the Ph2 -BINOLate ligand. Positioning of the nitrogen
Figure 16 Activation of a chiral catalyst with an achiral or meso stereocenters in close proximity to the zinc binding site
ligand with chiral conformations can result in an increase in the is expected to have a significant impact on the catalyst
enantioselectivity of the catalyst enantioselectivity in the asymmetric CC bond forming
16 ASYMMETRIC SYNTHESIS BY HOMOGENEOUS CATALYSIS
3 30 (R)
N N
4 66 (R) 74 (R)
Cl N N Cl
Cl Cl
5 75 (R) 87 (R)
N N
Mes Mes
6 Cl Cl 54 (R)
N N
Cl Cl
a
Reactions employed 10 mol% Ph2 -BINOL, 10 mol% diimine ligand, and 300 mol% diethylzinc.
Ar
Ar
N
N
O Zn O Zn
O O
N
N
Ar
Ar
Figure 17 Diastereomeric catalysts derived from different conformations of the diaminobiphenyl ligand
process. Examination of secondary diamines (Table 5, entries Diamines with pendent biphenyl groups were also
3 5) in Figure 16 resulted in generation of the secondary employed in the asymmetric addition reaction in Figure 16
alcohol with up to 76% enantioselectivity. This is the highest (Table 5, entries 6 and 7). It was predicted that atropisomer-
enantioselectivity obtained for the (S)-enantiomer in these ization of the biphenyl moiety in these ligands would have a
investigations. low barrier. Interaction of the stereochemically label biphenyl
ASYMMETRIC SYNTHESIS BY HOMOGENEOUS CATALYSIS 17
N N
7 83 (R) 92 (R)
N N
a
Reactions employed 10 mol% Ph2 -BINOL, 10 mol% diimine ligand, and 300 mol% diethylzinc.
moiety with the (Ph2 -BINOLate)Zn center is expected to combined with diethylzinc and benzaldehyde (no added Ph2 -
influence the biphenyl stereochemistry and extend the chiral BINOL). After 2 h it was determined that the reaction with the
environment of the resulting catalyst. diimine proceeded to 20% conversion. The reaction with the
The catalysts prepared with atropisomeric ligands in entries meso diamine was 51% complete in 2 h. Use of Ph2 -BINOL
6 and 7 gave the product with enantioselectivities as high as with the diimine or meso diamine resulted in a considerable
92% at 45 C. It is interesting to note that catalysts derived increase in the TOF, with both reactions reaching completion
from these ligands exhibited greater enantioselectivity than in under 15 min.59 These observations indicate that the achiral
when N,N,N ,N -tetraethylethylene diamine was employed ligands have a great impact on the catalyst reactivity as well
(Table 5, entry 2). Taken together, the results in Tables 4 and as the catalyst enantioselectivity.
5 clearly indicate the benefit of screening achiral ligands on The catalytically active species in these asymmetric
catalyst enantioselectivity. addition reactions are believed to be 4-coordinate (Ph2 -
The impact of achiral ligands on the TOF of the catalyst BINOLate)Zn(diimine) and (Ph2 -BINOLate)Zn(diamine)
in this system was then examined by following reaction complexes. Support for this hypothesis was gained
conversions with various catalysts. In the absence of both Ph2 - by synthesis and structure determination of the (Ph2 -
BINOL and diamine ligands, the reaction of diethylzinc with BINOLate)Zn(diamine) incorporating the N ,N -di-tert-butyl
benzaldehyde is very slow, exhibiting about 1% conversion diamine. The structure of this compound is illustrated
after 8 h at 0 C. When Ph2 -BINOL was employed in the in Figure 18. This catalyst likely coordinates the alde-
asymmetric addition to this substrate, the catalyst TOF hyde substrate generating a 5-coordinate zinc species with
increased exhibiting 25% conversion after 2 h. To evaluate the an activated aldehyde. Addition of the ethyl group from
TOF of zinc centers bearing diimine derived from ethylene ZnEt2 , possibly by a pathway that involves coordination
diamine and 2,4,6-trimethylbenzaldehyde (Table 4, entry 5) of the ZnEt2 to a BINOLate oxygen, results in product
or the meso diamine (Table 5, entry 7), these ligands were formation.
18 ASYMMETRIC SYNTHESIS BY HOMOGENEOUS CATALYSIS
3.7.2 Use of achiral additives without chiral conformations 3.7.3 Metal Geometry-Induced Ligand Asymmetry
The addition of achiral additives lacking chiral con- Ligand binding modes can play an important role in the
formations to asymmetric catalysts can enhance catalysts enantioselectivity of a catalyst. Some ligands are symmetric
enantioselectivity.62 The exact nature of the interaction in certain metal geometries, but become asymmetric when
between the additive and the chiral catalyst, however, is the metal binds to an additional ligand. This property can be
often not clear. The additives usually contain Lewis basic particularly useful in asymmetric catalysis if the achiral ligand
groups, and can behave as ligands by coordinating to catalysts adopts an asymmetric binding mode upon coordination of the
and changing the metal geometry and/or catalyst aggregation substrate. Under these circumstances the achiral ligand can
state. impact the chiral environment of the catalyst, changing the
NR3
H
Me N Me
O
Me
Yb(OTf)3 + (R )-BINOL Yb(OTf)3
2.4 equiv.
1.2 equiv. O
H
NR3
Figure 19 Preparation and proposed structure of chiral Yb(III) triflate Lewis acid
ASYMMETRIC SYNTHESIS BY HOMOGENEOUS CATALYSIS 19
R
((R )-BINOL)Yb(amine)2+3
O
20 mol%
O O
CO N O
O O
N O
(2S, 3R ), 93% ee.
N O 20 mol% 77%, endo /exo 89/11
O
((R )-BINOL)Yb(amine)2+3 R
20 mol%
CO N O
O O
enantioselectivity. An example of such a system is illustrated The objective of this study was to use the chirality of the
in the following paragraphs. (MBP)Ti metallocycle in the trigonal bipyramidal geometry
Compounds of the type (MBP)TiX2 (MBP = methylene to bias the chiral environment of an enantioselective catalyst.
bis(phenoxide) and X = Cl, Figure 21) are achiral, because Theoretically, if it were possible to replace the THF in one
they possess a plain of symmetry. Upon coordination of a of the enantiomers of (MBP)TiCl2 (THF) for a substrate, the
Lewis basic ligand L, however, a 5-coordinate (MBP)TiCl2 (L) (MBP)Ti metallocycle would provide a chiral environment
complex is generated. The apical and equatorial oxygens may for the substrate. Attack on the bound substrate by an achiral
be inequivalent by virtue of their binding sites (Figure 21). As reagent would generate a non-racemic product. Substitution of
a result, the (MBP)Ti metallocycle is chiral and (MBP)TiCl2 chiral, enantioenriched ligands for the chlorides would cause
(THF) exists as a racemic mixture.65 the configuration of the (MBP)Ti metallocycle to be biased.
If the biasing of the enantiomeric forms of the (MBP)Ti
metallocycle is efficient, this metallocycle might adopt a single
R enantiomeric form (Figure 21). In this study, readily available
R chiral alkoxide ligands were used to introduce asymmetry into
L
the catalyst.
O
A series of achiral derivatives of MBP-H2 (20 mol%) were
R CH2 Ti X used with Ti(OR )4 derived from the (S)-enantiomer of 1-
R L O phenyl-1-propanol in the asymmetric addition to aldehydes
X
O R (Figure 22). The results of this study are compiled in Table 6.
X Inspection of the enantioselectivities using various (MBP)Ti-
CH2 Ti R X = Cl
derivatives clearly illustrates that addition of different achiral
X R X = OR*
O MBP ligands can have a significant impact on the ee of
R the product [9% (R) to 83% (S)]. MBP-H2 ligands with
R L
O X small R groups were found to be less enantioselective.
R
CH2 X Nonetheless, when R = H (entries 1 and 2, Table 6), the
Ti
X = Cl catalysts exhibited significant differences in enantioselectivity
X = OR* O L from that of the background reaction in entry 10 [9% ee
R (R) vs. 39% ee (S)]. In this example, the background
R reaction is promoted by the chiral alkoxide complex Ti(OR )4 .
Increasing the bulk of the MBP ligand to R = t-Bu resulted in
Figure 21 When X = Cl, L = THF two enantiomeric 5-coordinate
an increase in enantioselectivities (entries 6 8). A further
titanium centers are possible. When X = OR and L = aldehyde increase in ee was observed when R = adamantyl (83%
substrate, diastereomeric 5-coordinate titanium complexes may form ee, entry 9). Thus, modification of the achiral MBP ligand
20 ASYMMETRIC SYNTHESIS BY HOMOGENEOUS CATALYSIS
OH OH
R R
20 mol%
R R
R + R
Ti(OR*)4
(MBP)Ti(OR*)2 HO Et
PhCHO + Ti(OR*)4 + ZnEt2
(1 eq) (3 eq) (1.2 eq) CH2Cl2 /Hexanes
Ph H
20 C
Et
OR* = O H
Tol
R R
R R
1 H H H 1 (S) Ar
2 H H Cl 9 (R) Ti
3 Cl Cl Cl 24 (S) O4
O1
4 Me H Me 16 (S)
5 Ph H H 36 (S) O3
6 t-Bu H t-Bu 68 (S)
7 t-Bu H Me 79 (S) Ar
8 t-Bu H H 73 (S) N1
9 Adamantyl H Me 83 (S)
10 NO MBP-H2 Ligand added 39 (S)
a
ee determined after 1 h of reaction. Figure 23 ORTEP drawing of (MBP)Ti(OR )2 (HNMe2 ). The aryl
groups have been removed for clarity
resulted in a change in ee of over 90% between entries 2 asymmetry can be applied to optimization of other asymmetric
and 9. catalysts.
As shown in this example, substrate binding may increase
the number of stereochemical elements in a catalyst. In these
investigations, it is proposed that a change in metal geome- 3.8 Combinatorial Methods for Catalyst Generation
try from tetrahedral to trigonal bipyramidal on coordination
of a substrate can induce chirality in the (MBP)Ti metallo- Combinatorial chemistry has been successfully employed
cycle (Figure 21). Once in an asymmetric binding mode, the in the search for new drug candidates, and has had a
(MBP)Ti moiety can contribute to, or even dominate, the relay significant impact on the pharmaceutical industry. High
of asymmetry to the substrate. The asymmetry of the bound throughput strategies allow the simultaneous generation of
MBP ligand is illustrated in the ORTEP diagram in Figure 23. many compounds. The idea of using such methods for the
An N ,N -dimethylamine plays the role of a substrate ana- synthesis and screening of chiral ligands and catalysts is
log in this example. The principle of geometry-induced ligand an attractive, yet formidable challenge. Three issues to be
ASYMMETRIC SYNTHESIS BY HOMOGENEOUS CATALYSIS 21
considered in designing catalyst systems for high throughput Table 7 Optimization of modular ligands for the asymmetric
screening are (1) sources of diversity, (2) catalyst synthesis, conjugate addition reaction
and (3) catalyst screening.66
Modular ligands and catalysts are ideal for high throughput N AA1 AA2 NHBu
screening. They are composed of subunits that can be easily
interchanged to generate large numbers of catalysts with a PPh2
wide range of steric and electronic properties. In metal-based O O
catalyst, the metal can also be varied, providing additional 5 mol% (CuOTf)2C6H6
12 mol% chiral ligand
diversity. i Pr i Pr
ZnEt2, toluene, 4 C, 24 h
One of the requirements of this approach is that catalyst
synthesis must be accomplished with clean, high-yielding Et
reactions to avoid time-consuming purification steps. This Ligand AA1 AA2 conv. ee (%)
requirement often limits the classes of ligands and catalysts
that are amenable to high throughput methods. L1 L-t-Lue L-Phe 93 85
Assaying the enantioselectivity and activity of individual L2 L-Val L-Phe 32 76
L3 L-t-Lue Gly 87 93
catalyst is often the most difficult and time-consuming aspect L4 L-Val Gly 92 91
of high throughput screening. Most reports involve screening L5 L-t-Lue 98 83
each catalyst individually L6 L-Val 97 96
Ligands incorporating amino acids fulfill these guidelines Me Me
and have been used to develop highly enantioselective
catalysts for several reactions. A series of peptide-based NHBu
N
catalysts for the asymmetric conjugate addition of organozinc
O
reagents to enones has been reported. Closely related ligands PPh2
derived from dipeptide phophine ligands have been shown L6*
to give excellent enantioselectivities for cyclic enones67
(equation 12) and acyclic enones.68 However, these ligands
were not optimal in the conjugate addition of trisubstituted Table 8 Cu-Catalyzed conjugate addition reaction with ligand L6
enones.69 (6 12 mol%) with ZnR2 . Products were obtained with good to
excellent diastereoselectivity favoring the anti diastereomer
Me
Me Me O O
O
H
N n-hex n-hex R= Me 95
N NHBu Et 97
O R
PPh2
L1*
O-tBu O O
O (1) mol% CuOTf R O
(2) 45 mol% L1* Me Me R= Me 97
+ ZnR2 Et 97
R Me R Me iPr 98
6993% yield R
9995% ee
(12) O O
Me Me 98
In developing new ligands for these substrates, the points
of diversity are the amino acid residues (AA1 and AA2), Et
the substituents on the phosphine and the metal center
(Table 7). Each of these subunits can be varied, leading to
a large number of catalysts. Variation of the amino acids was glycine for the phenylalanine in both L3 and L4 resulted
explored, because peptidic systems can be easily prepared in an increase in enantioselectivity in each case. Dropping
in parallel by solid phase protocols. As shown in Table 7, that amino acid residue resulted in the optimal catalyst in this
ligand L1 which was successfully used with cyclic enones study.
(equation 12) gave 85% ee. Substitution of tert-leucine for As seen in Table 8, the resulting catalyst system gave excel-
valine led to a decrease in enantioselectivity and a significant lent enantioselectivities with a range of enones and dialkylzinc
loss in efficiency (L2 ). Surprisingly, substitution of an achiral reagents.
22 ASYMMETRIC SYNTHESIS BY HOMOGENEOUS CATALYSIS
This example illustrates how screening peptide-based 8. T. P. Yoon and E. N. Jacobsen, Science, 2003, 299, 1691.
ligands can be useful in the development of catalysts. 9. W. Zhang, J. L. Loebach, S. R. Wilson, and E. N. Jacobsen, J.
These catalysts could not be rationally designed based on Am. Chem. Soc., 1990, 112, 2801.
related ligands or understanding of the mechanism. Related 10. R. Irie, K. Noda, Y. Ito, N. Matsumoto, and T. Katsuki,
nonmetal-based catalysts employing peptide-based ligands Tetrahedron Lett., 1990, 31, 7345.
have also been optimized using these techniques. These studies
11. T. Katsuki, in Catalytic Asymmetric Synthesis, 2nd ed., ed.
employed large libraries of compounds.70
I. Ojima, Wiley-VCH, New York, 2000, p. 287.
12. E. N. Jacobsen and M. H. Wu, in Comprehensive Asymmetric
Catalysis, eds. E. N. Jacobsen, A. Pfaltz, and H. Yamamoto,
Springer, Berlin, 1999, Vol. 2, p. 649.
4 FINAL PERSPECTIVE
13. H. Nishikori, C. Ohta, and T. Katsuki, Synlett, 2000, 1557.
14. A. M. Daly, M. F. Renehan, and D. G. Gilheany, Org. Lett.,
This brief summary of alternative approaches to asymmet-
2001, 3, 663.
ric catalysis is not meant to be complete or comprehensive.
There are many excellent examples that could have been 15. K. Nakata, T. Takeda, J. Mihara, T. Hamada, R. Irie, and
included in this work and would have served equally as well. T. Katsuki, Chem. Eur. J., 2001, 7, 3776.
Nonetheless, the goal of this section is to expose the reader 16. J. M. Keith, J. F. Larrow, and E. N. Jacobsen, Adv. Synth. &
to concepts in catalyst design and optimization that have not Catal., 2001, 1, 5.
been extensively explored and to inspire those interested in 17. S. E. Schaus, B. D. Brandes, J. F. Larrow, M. Tokunaga,
pursuing investigations in this area to take a nontraditional K. B. Hansen, A. E. Gould, M. E. Furrow, and E. N. Jacobsen,
approach. J. Am. Chem. Soc., 2002, 124, 1307.
18. M. Tokunaga, J. F. Larrow, F. Kakuichi, and E. N. Jacobsen,
Science, 1997, 277, 936.
19. L. Aouni, K. E. Hemberger, S. Jasmin, H. Kabir, J. F. Larrow,
5 RELATED ARTICLES I. Le-Fur, P. Morel, and T. Schlama, in Asymmetric Catalysis
on Industrial Scale, eds. H. I. Blaser and E. Schmidt, Wiley-
Actinides: Inorganic & Coordination Chemistry; Boron: VCH, Weinheim, 2004, p. 165.
Inorganic Chemistry; Hydrogen Bonding & Dihydrogen 20. J. F. Larrow and E. N. Jacobsen, J. Am. Chem. Soc., 1994, 116,
Bonding; Palladium: Organometallic Chemistry; Platinum: 12129.
Organometallic Chemistry; Rhodium: Organometallic Chem- 21. T. Hamada, R. Irie, J. Mihara, K. Hamachi, and T. Katsuki,
istry; Ruthenium: Organometallic Chemistry; Titanium: Tetrahedron, 1998, 54, 10017.
Organometallic Chemistry; Zinc: Inorganic & Coordination 22. M. Palucki, P. Hanson, and E. N. Jacobsen, Tetrahedron Lett.,
Chemistry; Zinc: Organometallic Chemistry. 1992, 33, 7111.
23. K. Noda, N. Hosoya, R. Irie, Y. Yamashita, and T. Katsuki,
Tetrahedron, 1994, 50, 9609.
24. H. Nishikori and T. Katsuki, Tetrahedron Lett., 1996, 37, 9245.
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Beryllium & Magnesium: their important reactions include nucleophilic displacement of
less basic leaving groups from saturated carbon atoms or other
Organometallic Chemistry elements, addition to carbonyl groups and other unsaturated
functions, and nucleophilic substitution at the acyl group of
carboxylic acid derivatives. They also can transfer an electron
Dovas A. Saulys1 & E. Alexander Hill2 as a reductant.
1
University of Wisconsin, Madison, WI, USA In contrast, organoberyllium compounds are not as easily
2
University of Wisconsin, Milwaukee, WI, USA prepared by direct reaction of beryllium metal with organic
substrates. They are less nucleophilic than their magnesium
Based in part on the article Beryllium & Magnesium: Organometallic congeners, and have not found a unique niche in organic or
Chemistry by E. Alexander Hill which appeared in the Encyclopedia organometallic synthesis. The high toxicity of beryllium and
of Inorganic Chemistry, First Edition. its compounds is likely responsible for the latter. There is,
however, a substantial body of interesting chemistry, and it is
1 Introduction 1 useful to contrast the chemistry of magnesium compounds with
2 Bonding and Structure 1 their lighter analogs. Indeed, synthetic beryllium research is
3 Spectroscopy 6 currently experiencing a revival, after decades of little activity.
4 Preparation 7 Important new work on substituted beryllocenes, as well as
5 Reactions of Organoberyllium and -Magnesium the advent of beryllium silicon chemistry are discussed in
Compounds 11 Sections 6.4 and 6.7, respectively.
6 Special Classes of Compounds 21 The classic monograph of Kharasch and Reinmuth,2 with
7 Related Articles 25 its voluminous tables, is still a useful source of information on
8 References 26 organomagnesium chemistry. General surveys have appeared
in Comprehensive Organometallic Chemistry,35 in The
Chemistry of the Metal Carbon Bond,6 and elsewhere.7
Glossary Especially noteworthy are two recent compilations that
cover virtually every aspect of Grignard chemistry.8,9 The
Barbier reaction: reaction of an organic halide with a most recent surveys of organoberyllium chemistry are in
substrate and metal Comprehensive Organometallic Chemistry II,10 and the
Grignard reaction: reaction of a preformed organometal- dedicated volume of the Gmelin series.11 Details not explicitly
lic solution referenced may also be found in these general reviews; reviews
Grignard reagent: in this article, will refer to the solution pertinent to limited aspects are referenced in relevant locations
prepared by reaction of an alkyl halide with magnesium metal, herein. In the case of serial compilations, the latest edition is
without implication as to molecular species actually present generally cited.
bridge via electron-deficient multicenter bonds (see Electron complexes are also monomeric, and exhibit a trigonal planar
Deficient Compound and Multicenter Two-electron Bonding). coordination geometry for magnesium when R is sterically
In any given instance, the actual structure, degree of associa- demanding (e.g. R = t-Bu).22
tion, and coordination number of the metal will be a function
of the basicity of the solvent, the coordinating/bridging ten-
dencies of the Y and organic groups, the acidity of the R
metal center (as influenced by the electronegativities of the N N
attached groups), and the steric requirements of the various Me3Si R
SiMe3
Me3Si +
components (see Coordination Numbers & Geometries). In Mg H B N N Mg Me
SiMe3
general, THF (tetrahydrofuran) is more basic and less bulky Me3Si SiMe3 N N
than Et2 O, (i-Pr)2 O coordinates less strongly, and Chelating
Ligands bind strongly. F and Cl bridge more effectively R
than the higher halides, and among organic groups, methyl
and alkynyl are good bridging groups (Me2 Mg is reported to (1) (2)
crystallize solvent-free from diethyl ether).
Recent reviews have surveyed X-ray and electron
2.3 Solvent-free Aggregates and Polymers
diffraction structures of organomagnesium compounds12,13
(see Diffraction Methods in Inorganic Chemistry); literature Solid unsolvated Me2 Be, Me2 Mg, and Et2 Mg have
citations for both metals are also included in other reviews.4,8,9 polymeric linear chains of metal atoms linked by bridging alkyl
groups (3) oriented in a distorted tetrahedron around the metal.
2.1 The Metal-to-carbon Bond The bond distances (CMg, 224 and 226 pm; CBe, 193 pm)
are longer than in the monomer, since one-electron pair is
The electronegativities of beryllium and magnesium on shared between two bonds in the electron-deficient bridge.
various scales lie in the vicinity of 1.6 and 1.35, respectively, The M2 C2 rings have small angles at the carbon (75 , 72 , and
substantially less electronegative than carbon at about 2.55 66 ) that maximize overlap of the single carbon orbital with
(see Electronegativity). Simple CBe and CMg bonds should orbitals on the two metal atoms. Higher homologs are usually
therefore be quite polar, with Pauling ionic characters associated as dimers or small oligomers in noncoordinating
of about 20 and 30% respectively (see Ionic Character). solvents, and mass spectra indicate some association of
Molecular orbital calculations (see Molecular Orbital Theory) alkylberylliums even in the gas phase. Ph2 Mg also crystallizes
also indicate highly polar, perhaps essentially ionic, CMg and in polymeric chains with the phenyl rings perpendicular to
CBe bonds, though specific conclusions vary depending on the chain direction (CMg, 226 pm). Magnesium acetylides
the basis set, type of calculation, and the interpretation.1417 containing a cubic Mg4 (3 -C)4 core have recently been
Thermochemical data on organoberyllium and -magnesium prepared; they are the first MgR2 compounds to exhibit this
compounds are not very extensive. A number of enthalpies typically organolithium-type structural motif.23
of formation for Grignard reagents have been determined
via measurement of their heats of hydrolysis,18,19 and bond
dissociation energies have been measured for Np2 Mg.20 An R R Et
R
attempt has also been made using theoretical calculations Mg Mg Mg OEt2
Mg Mg
in combination with experimental data to develop a set R R OEt2
R Br
of consistent Bond Energies for lithium, beryllium, and n
Several magnesium and beryllium compounds, includ- Additional coordination sites in the monomer may be
ing Cp2 Mg, Cp 2 Mg, Cp(Np)Mg, Np2 Mg, MgBr2 , MgI2 , occupied by solvent molecules. Besides solvation by ethers,
Cp(Me)Be, Me2 Be and (t-Bu)2 Be have been studied in the gas complexes with a variety of other donors have been
phase. All have the linear geometry predicted for sp Hybridiza- studied in solution or isolated, and a number of crystal
tion at the metal, as do the extremely hindered (1), as well as structures have been reported. Among oxygen ligands, HMPA
(tert-Bu3 Si)2 Be (Section 6.7), in the crystal. CMg and CBe (hexamethylphosphoramide) is especially basic. In general,
Bond Lengths are 211.6 212.6 and 169.8 170.6 pm, respec- nitrogen as a ligating atom is more basic than oxygen,
tively. Some [tris(pyrazolyl)hydroborato]metal derivatives though frequently more hindered, and sulfur is weaker. The
(see Tris(pyrazolyl)borates) are unsolvated monomers, with chelating diamine TMEDA (tetramethylethylenediamine) is
approximately tetrahedral geometry about the metal (e.g. (2); particularly noteworthy for forming stable, monomeric, and
CMg, 212 pm; CBe, 170.8).8 Certain -diketiminateMgR often sublimable crystalline complexes. Potential ligands such
BERYLLIUM & MAGNESIUM: ORGANOMETALLIC CHEMISTRY 3
L Br Et
An operational description is that one reactant (the more
Mg Mg ionic compound with the more electropositive metal) transfers
Et Br L alkyl anions to the other. Thus the four methyl groups in
(10)
Li2 BeMe4 form a distorted tetrahedron around the beryllium,
with longer distances to the lithium ions. However, this
description is oversimplified. The low-temperature nuclear
tetramers are common; (MeBeOSiMe3 )4 has the cubane magnetic resonance (NMR) spectrum of Li3 MgMe5 has
structure (11), and other Be and Mg tetramers are probably three different methyl resonances, suggesting structure (14),
similar. Other degrees of association (dimer, trimer, polymer) related to the MeLi tetramer. Ate complexes with zinc and
are found. Solvated RMgOR and RMgSR complexes are aluminum compounds also form. Electron-deficient bridge-
often dimeric. Coordinated solvent is lost more easily bonded structures, exemplified by the X-ray structure of
from RMgOR than from analogous Grignard reagents. (15), are generally proposed. NMR studies show rapid
Dialkylamido groups also bridge strongly. Unsolvated intramolecular and intermolecular exchange processes, and
compounds RMNR2 tend to form dimers and trimers (Be), equilibrium with the constituent organometallic compounds.
probably with tricoordinate metal as in (12). Solvated Methyl, ethyl, or phenyl has usually been the organic group;
monomers, dimers, and polymeric aggregates have been bulkier alkyl groups are less inclined to participate. Compound
demonstrated. An internally coordinated dimer (13) is formed (16) is an unusual internal ate complex.10,11
in the reaction of R2 M with MeNHCH2 CH2 NMe2 .
Me
R R R R R Mg Me
Me Me
O M Me Me Me Me
R N
M O Li Li Al Mg Al
R Be Be R
R M O Li Me Me Me Me
O M R N Me
R R R (14) (15)
R
(11) (12)
Me2 _
+ P+ BH
Me2P 2
Me _
H2B M2 +
+
PMe2
N Me
Me2HP
Me2N M NMe2
M (16)
Me MeN
Alkali hydride ate complexes also exist, including
(13)
MR2 BeH, MR2 MgH, and other compositions, although it
appears that KR2 MgH compounds are unstable with respect
Organomagnesium hydrides (RMgH) with THF solvation to KR3 Mg and MgH2 26 Structural features include hydride
are stable. They form dimeric and oligomeric structures bridges and electron-deficient bonding to the alkali metal. In
associated through bridging hydrides. a dimer of NaEt2 BeH, the bridging hydrides bind also to the
ether-solvated sodium atoms. Ate complexes are also formed
in reactions with diborane, NaBH4 , AlH3 , and (Li/Na)AlH4 .
2.6 Ate Complexes
to yield a MgX2 R2 M complex. Subsequently, exchange was exchange between R2 Mg or R2 Be and an alkoxide is often a
indeed demonstrated, and additional evidence has thoroughly useful synthesis for RMOR .4,10
confirmed the reality of the equilibrium.25,27
MgX2 + R2 Mg
2.8 Ionization
2RMgX (1)
to the strain of a planar carbon in the three-membered ring. The 13 C resonance of the -carbon of an organomagnesium
Interconversion of the diastereomers of (18) is also measurably compound is also shifted to high field, but not so distinctively.
slow.29 The faster inversion rates of primary CMg bonds may A substantial body of data has been tabulated,3032 and
be studied by NMR lineshape techniques. The -hydrogens correlation equations have been given which are reasonably
of (19) are magnetically nonequivalent, but are interconverted successful at predicting -, -, and -shifts based on
by inversion of configuration.8 The rate is second order in those of the corresponding hydrocarbon.33,34 In an aryl-
monomeric organomagnesium, faster in diethyl ether than in or vinylmagnesium compound, the sp2 -carbon resonance
THF, and faster for Cl than Br . These observations are appears at quite low field (164 ppm for PhMgBr); ortho
consistent with a mechanism in which inversion occurs during carbons and the central carbon of the allyl group in
transfer or exchange of the alkyl group between magnesiums. allylmagnesium bromide are also deshielded.
Inversion is much slower than the total rate of exchange, which Although quite broad, 25 Mg resonances of organomagne-
occurs predominantly with retention. Recently, stereospecific sium compounds have been reported.35 The shift is sensitive to
exchange of the sulfoxide of an enantiomerically pure solvation and ligand electronegativity, and resonances for the
-chloroalkylsulfoxide for a magnesium, and subsequent Schlenk equilibrium species have been reported. Beryllium-9
carbenoid homologation (a reaction step that avoids free NMR spectra are more informative than those of 25 Mg.36 In
radical intermediates) has been used to prepare a chiral addition to a broader chemical shift range, a much smaller
(93% enantiomeric excess), non- -heteroatom stabilized quadrupole moment makes for narrower line widths, allowing
Grignard reagent, (20) (equation 3). (20) is generated as one observation of couplings with other elements (e.g. 1 H, 13 C,
11
component of a mixture of Grignard reagents and sulfoxides, B, 19 F, 29 Si, 31 P).
and racemizes with a half-life of five hours at 10 C.29
of associated species with up to eight Be atoms, and associated with fresh solvent. Formation of a difficult Grignard reagent
species are also seen in the spectra of Et2 Be and Ph2 Be. may be helped by entrainment: carrying out the reaction in
admixture with a reactive halide. 1,2-Dibromoethane is often
preferred, as it affords only ethylene and MgBr2 . Impurities
in the magnesium, amalgamation, or transition metal salts
4 PREPARATION may be activating, but may also decrease the yield or affect
subsequent reactions. For mechanism studies, extremely high
purity magnesium obtained by sublimation or zone refining
4.1 Direct Reaction of Organic Halogen Compounds may be used.
with the Metal A number of specially reactive forms of magnesium
The classical method for formation of a Grignard reagent, as have been used to reduce induction periods, and also for
originally described by Victor Grignard in 1900, is the reaction unreactive halides or low reaction temperatures. They include
of an organic halide in ether solution with magnesium metal metal slurries made by reduction of a magnesium salt by
(equation 4). Typically, this is an exothermic reaction but, as a potassium or lithium metal (Rieke magnesium), lithium
heterogeneous process, one which may not start immediately. naphthalene, or potassium-intercalated graphite, and finely
The Grignard reagent is sensitive to moisture and oxygen. divided metal produced by condensation of magnesium vapors
in an organic solvent.8 The anthracene magnesium complex
RX + Mg RMgX (4) (see Section 6.3) may be used in stoichiometric amount as a
magnesium source or as a catalyst, or pyrolyzed to deposit a
In the customary procedure, the magnesium is placed in reactive magnesium residue.8,9
a dried apparatus under an inert atmosphere of nitrogen or The most common solvents for preparation of Grignard
argon. The magnesium may be activated (if necessary), and reagents are diethyl ether and THF. The latter is especially
a small portion of the halide is added to initiate the reaction useful for making Grignard reagents from aryl and vinyl
in concentrated solution. The remainder of the halide in more halides, particularly the relatively unreactive chlorides. A
dilute solution is added at a rate sufficient to maintain the number of other ethers (e.g. butyl, isopentyl, anisole),
desired temperature (often reflux). Cooling may be needed HMPA, and tertiary amines have also been used. Although
to moderate the reaction after initiation. Stirring or heating a coordinating solvent is generally needed for their facile
is often continued longer to assure complete reaction, and formation, it is possible to prepare many Grignard reagents
in the case of less-reactive halides it may be necessary to in hydrocarbon solvents in the presence of a molar (or less)
heat throughout an extended reaction period. Commercial equivalent of coordinating base: 1M toluene solutions have
magnesium turnings sold specifically for Grignard reagents been prepared.37 The degree of solvation of a Grignard
are usually satisfactory, and the reaction frequently starts reagent influences its reactivity, a phenomenon that will be
vigorously with gentle warming after a short induction period. briefly described here. Additions of Grignard reagents to
Carefully dried solvents improve ease of formation and ketones and nitriles, ligand substitution with alkoxysilanes,
minimize loss of the reagent by hydrolysis. and oxirane ring openings proceed faster in less-nucleophilic
The solution so obtained is usually used directly in synthetic ethers; rates decrease in the order: t-Bu2 O > Et2 O > THF.
applications, frequently without even separation from excess Partial replacement of ether by toluene accelerates the
magnesium. Otherwise, the reagent may be transferred by rate of reaction of Grignard reagents with hydrazones, 1-
syringe, cannula, or decantation and filtration, or modified alkynes, alkylethoxysilanes (but not with alkylchlorosilanes),
by replacement of the solvent or addition of other reactants and increases the ratio of addition to reduction product
or catalysts. (Section 5.6.1) with ketones. These effects are attributed to
The magnesium is critical to the success of a Grignard the greater ease of coordination of substrate to Grignard
reagent preparation. An oxide film or other surface blockage reagent in solvents of lower solvating ability, although the
may cause an induction period by excluding halide from the situation for ketones is more complex.37,38 Additives or
underlying magnesium surface. There are numerous recipes cosolvents, typically bases or unsaturated species, are often
for activation, which apparently remove or break through used to increase yields or enhance selectivity, especially in
this film. Physical activation may be achieved by crushing or reactions mediated by transition metals (see Sections 5.4
grinding the magnesium turnings or prolonged stirring without and 5.5). The relatively (vs. e.g. HMPA) inexpensive and
solvent.8,9 Sonication helps remove absorbed water, shortens low-toxicity 1-Methyl-2-pyrrolidinone, NMP, is increasingly
the induction period, and increases the subsequent rate.8,9 popular.
Variously recommended chemical activation pretreatments8,9 Unsolvated Grignard reagents have also been formed
include heating dry with a small amount of iodine, stirring by cocondensation of magnesium vapor with the organic
with a preformed Grignard reagent solution, or reaction halide at low temperature, and allowing the resulting
with one of a variety of activating reagents, for example, matrix to warm.9 Cluster Grignard reagents, PhMg4 X,
Br2 , AlBr3 , Si(OEt)4 . The magnesium may then be washed (X = F, Cl, Br), theoretically predicted to be stable, have
8 BERYLLIUM & MAGNESIUM: ORGANOMETALLIC CHEMISTRY
been similarly prepared, and characterized by MALDI-TOF solvent attack, coupling, and isomerization, for example,
(matrix-assisted laser desorption/ionization-time of flight) cyclization of the 5-hexenyl radical (21) to the cyclopentyl-
mass spectrometry and elemental analysis. The identities and methyl radical (22). The rate of reaction is proportional to
ratios of hydrolysis/deuterolysis products confirm the presence the concentration of organic halide in solution and to the
of MgC and MgMg bonds (equation 5). Most recently, surface area of the magnesium. With iodides and more reac-
room temperature transmetalation reactions in solution have tive alkyl bromides, for example, cyclopentyl, the rate is
been used to prepare the analogous alkyl derivatives from affected by mass transport, but other bromides and chlo-
the phenyl reagents and alkyl halides. This work has rides react at a rate controlled by chemical processes at the
implications for the mechanism of Grignard reagent formation surface.9,40
(Section 4.2)39
4.3 Formation by Exchange with Previously Formed exchange with a more active metal. This reaction is useful for
Organometallic Compounds making R2 Mg compounds from mercury or (less commonly)
zinc or silicon alkyls. The product is free of the traces of
4.3.1 Alkylation of a Beryllium or Magnesium Salt halide or dioxane which may remain when magnesium halide
is precipitated from a Grignard reagent, and in hydrocarbon
Exchange generally occurs between the organometallic solvents unsolvated R2 Mg is formed. A modification produces
compound of an electropositive metal and the salt of RMgX compounds. Beryllium appears to be less reactive, but
a less electropositive one. This reaction is effectively a does behave similarly. Examples are given in equations (10)
nucleophilic substitution by the organometallic carbanion on and (11).
the electrophilic metal center, resulting in formation of a more
ionic salt and a more covalent organometallic compound. Mg
MgBr Hg Mg (10)
In this method, organoalkali starting materials may serve as 2 THF 2
the alkyl source. Organolithium compounds are most used
several Mg/MgBr2
because of their synthetic accessibility by routes which do RHg(CH2 )3 HgR
H2 C=C=CH2
not start with the organic halide. Organoberyllium compounds steps THF
may also be made starting with Grignard reagents. Illustrative BrMg(CH2 )3 MgBr (11)
examples are shown in equations (7) and (8). Essentially the
same process may be used to replace the halogen of RBeX or
RMgX, forming R2 Be or R2 Mg. 4.3.3 Metal Halogen Exchange
i-PrMgCl
It should be noted that the same class of reaction, in CBr4 CBr3 MgX (13)
which the organomagnesium compound serves as the source 75 C, THF
these are not formed quickly in ether solvents, but addition catalyzed reactions involve titanium hydride intermediates.
of HMPA markedly increases the reactivity; the less acidic
diphenylmethane reacts at 100 C. Some polyhalogenated Cp2TiCl 2
R + MgX R
MgX +
compounds are relatively easily metallated, as are aromatic
ring positions ortho to O or N substituents (equation 15) and (16)
some heteroaromatics. Magnesium amide bases, for example,
(24) or BuMgN(i-Pr)2 effectively magnesiate a variety of Terminal alkenes react relatively readily in ether (80 C)
substrates, the latter regioselectively.48 The alkyl amide and with RBeH, but internal ones are less reactive. The addition
s-BuMgBu are alkane soluble and commercially available. is slowed but not completely inhibited by coordination with
ether or NMe3 . Rearrangement of (t-Bu)2 Be to the i-Bu
s-BuMgBu compound occurs by BeH elimination and re-addition in the
2PhCCH (PhCC)2 Mg (14)
opposite sense.
EtMgBr
N N
N N (15) 4.5 Formation of R2 Mg
Mg
A number of methods discussed in the foregoing sections
Br
are specifically useful for forming R2 Mg compounds. These
include precipitation of magnesium halide from a Grignard
reagent, the transition metal-catalyzed reaction of active
(prepared with Mganthracene) MgH2 with terminal olefins,
NMgBr the reaction of a magnesium halide or Grignard reagent
with an organolithium, and exchange of a dialkylmercury
compound with magnesium metal. The relative merits of
(24) various methods have been discussed.49 Other methods of
narrower applicability include the Metalation of alkynes and
other acidic hydrocarbons with R2 Mg.
Abstraction of acidic protons to a carbonyl or nitrile
function can occur in competition with desired Grignard
addition reactions (see Section 5.6). In HMPA, this is the 4.6 Other RMY Compounds
major reaction, and is useful for preparing magnesium enolates
The reaction of R2 Be or R2 Mg compounds with one
of carbonyl compounds, sulfones, and so on.
equivalent of OH, SH, NH, or other acidic hydrogen leads
to compounds of the stoichiometry RMY. Variants include the
4.4 Addition of CMg and HMg to CarbonCarbon reaction of an alkyl chloride with magnesium and alcohol (or
Multiple Bonds NaOR ) in hydrocarbon solvent. MeBeCN has been prepared
from Me2 Be and HCN. Redistribution reactions of R2 M with
M(Y)2 have been used to form the alkoxides, thiolates, and
4.4.1 Carbometalation amides. The addition of R2 M to one equivalent of an aldehyde,
ketone, epoxide, or imine also leads to RMOR or RMNR2
Addition of an organomagnesium bond to an alkene, species (equation 17). Dialkylmagnesiums react like Grignard
alkyne, or a benzenoid ring generates a new organomagnesium reagents in alkylation and carbonyl addition reactions.
compound. With simple alkenes, addition occurs only under
strenuous conditions. This reaction will be discussed later, O OBeEt
with appropriate examples, as a reaction of organomagnesium Et2Be
(17)
compounds in the Section on Amides and Lactans.. Et Et Et Et
Et
RMgX H RMgX
Most of the chemistry of organoberyllium and -magnesium RH + + R
(19)
compounds is associated with the basicity of the organic O H O O
+MgX
MgX
groups bound to the metal, either in the Brnsted Lowry
or the Lewis (nucleophile) sense. Also associated with their
electron-rich character is the potential to function as reducing
agents by loss of an electron, and there is increasing evidence 5.2 Redox Chemistry
that many formally nucleophilic reactions occur, in fact,
by a mechanism involving electron transfer (see Electron In the electrolysis of ethereal Grignard reagent solutions,
Transfer Reactions: Theory). The metal atom is also an magnesium species migrate toward both electrodes. At the
electrophilic or Lewis-acidic site, and electrophilic interaction anode, one-electron oxidation produces organic radicals which
with the metal doubtless plays a role in many of their combine, disproportionate, react with solvent or other solutes,
nucleophilic reactions. or attack the electrode (e.g. Pb PbR4 ). Tertiary alkyls are
Shortly before the successful preparation of organomag- oxidized most easily, and methyl and phenyl least easily.
nesium compounds by Victor Grignard, his mentor, Philippe At the cathode, magnesium is deposited, and alkyl radicals
Barbier, had discovered that reaction of an aldehyde or ketone appear to be formed also. There are two reduction waves,
and an alkyl halide in the presence of magnesium metal led corresponding to MgX2 and RMgX.
to formation of an alcohol, essentially as in the Grignard Organomagnesium and -beryllium compounds are very
reaction. The use of the older technique, referred to as the sensitive to oxidation by air. The reaction appears formally
Barbier method or as the in situ reaction, holds advantages to be a simple addition to the OO bond. However, it
in some cases.8 is clearly established that Grignard reagents react by the
As noted previously, much less attention has been directed radical chain process shown in Scheme 1. The subsequent
to synthetic applications of beryllium organometallics. reaction to produce the alkoxide is less clear mechanistically.
Sulfur and selenium form analogous products. Grignard and
organoberyllium compounds may also be oxidized by other
5.1 Thermal Decomposition peroxides. Autoxidation of aryl Grignard reagents often is
accompanied by chemiluminescence resulting from emission
When a -hydrogen is present, decomposition may occur by biaryls.
by -Elimination of an alkene with formation of a MH In the Kharasch reaction (equation 20), Grignard reagents
bond (equation 18). Tertiary alkyl groups are most easily are in effect oxidized by organic halides in the presence of
eliminated. A polar, probably cyclic process is likely, but transition metal salts, most commonly cobalt. The Grignard
there is evidence for homolytic cleavage in the decomposition reagent produces mostly disproportionation products (or the
of (t-Bu)2 Mg. Hydrogen is subsequently formed at higher biaryl from ArMgX), and products from the organic halide
temperature. The decomposition of gaseous (t-Bu)2 Be is the are derived from the corresponding radical. It is likely that the
primary source of unsolvated BeH2 , which is of interest as a transition metal is alkylated by the Grignard reagent, and that
high energy propellant and as a fuel source for nuclear fusion the resulting intermediate decomposes by nonradical pathways
reactors. If -elimination of hydrogen is not possible, thermal to metal species which then abstract a halogen atom from the
stability is greater. Ph2 Mg decomposes at 280 C to biphenyl organic halide.
and magnesium metal. Me2 Mg and Me2 both decompose
above 200 C to yield methane and a residue (CH2 M)n .
R X
2RMgX RR or R(+H) + R(H) (20)
CoCl2
t-Bu2Be BeH2 + (18)
RMgX + O2 R + O2MgX
Appropriately located functional groups also lower the
R + O2 ROO
thermal stability. The preparation and stability of a number of
these is noted in Section 6.2. ROO + RMgX ROOMgX + R
Solutions of Grignard reagents also decompose at
RMgX + ROOMgX 2ROMgX
temperatures in excess of 100 C by attack on the solvent.50
From either diethyl ether or THF, ethylene is among the
products. In the latter case, the reaction follows two major Scheme 1
12 BERYLLIUM & MAGNESIUM: ORGANOMETALLIC CHEMISTRY
5.3 Reaction as a Brnsted Base: Formation of CH electronegative leaving groups are replaced by organic groups,
Bonds8 often allowing controlled replacement of leaving groups to
produce partially alkylated or mixed polyalkylated products.
Organometallic compounds of Be and Mg are hydrolyzed As noted, a bimetallic ate complex may be formed instead
by OH, NH, SH, and other hydrogens more acidic than the of a simple alkylation product. For example, addition of
conjugate acid of the R of the organometallic. In practice, Me2 Mg to ZnCl2 in excess of the stoichiometric 1:1 ratio
this reaction may be quite slow for weak carbon acids which forms the ate complex Me4 ZnMg. A particularly important
do not coordinate as ligands to the metal. The reaction has instance is with CuI halides. Complexes of stoichiometry
been discussed as the metalation reaction (Section 4.3.4) and RCuMgX2 or R2 CuMgX, referred to as Normant Complexes,
for the formation of RMY compounds (Section 4.6). It is also are useful reagents in organic synthesis (see Sections 5.5,
used for indirect reduction of organic halides to hydrocarbons 5.6.2, and 5.8). There are varied recipes, including other CuI
via conversion to the Grignard reagent and hydrolysis, and for salts, and Me2 S or P(OR)3 as additional ligands.6,8 An active
introducing a deuterium or tritium label. area of study is the catalysis of reactions of Grignard reagents
by transition metal salts or complexes. The active reagents
in these catalyzed reactions are undoubtedly transition metal
5.4 Nucleophilic Displacement at Atoms other than
species, produced via alkylation by the Grignard reagent.
Carbon: Alkylation
Many useful synthetic methods involve alkylation of
The organic group of an organometallic compound nonmetals by Grignard reagents. Displacement at a halogen
will alkylate another more electronegative element by leads to an organic halide. This reaction may be useful
displacement of halide or other suitable leaving group for replacing one halogen by another, for characterizing
(equation 21). The reaction is a nucleophilic displacement the organic group of a Grignard reagent, or when the
which derives its driving force from formation of the organomagnesium compound is formed in an indirect fashion.
more ionic product MXY. Organolithium and -magnesium The most obvious reagent for such a displacement is molecular
compounds, because of their ease of formation and the halogen itself, but it can lead to mixtures of products if
electropositive character of the metal, are most often used the halogen is different from that of the Grignard reagent.
for this purpose. Fewer examples have been reported with Organic halogen compounds may serve as alternative halogen
organoberyllium compounds, although they themselves are sources, for example, 1,2-dibromoethane, hexachloroethane,
often formed in this way (Section 4.3.1). N -chlorosuccinimide, or 1-chloro-2-iodoethane. Perchloryl
fluoride and N2 F2 have been used, but may present
RMgX + YZ RZ + MgXY (21)
explosion hazards.
Oxygen (see Section 5.2) and the other group 16
elements react with organomagnesium compounds. Some
Organomagnesium compounds are less reactive as other displacements at oxygen and sulfur are shown in
nucleophiles than organolithium compounds, it may be more equations (22 24).
difficult to separate products from the magnesium salts,
and the presence of halide and ether solvent in a Grignard ArMgBr + (EtO)2 BOO-t-Bu ArOH (22)
reagent can be disadvantageous. However, one may use the
O
dialkylmagnesium instead of a Grignard reagent, and work
with a hydrocarbon suspension rather than an ether solution. RMgCl + (CF3SO2)2O R S CF3 + CF3SO3MgCl (23)
The lower reactivity may be an advantage by allowing O
sequential partial alkylation, and the Grignard reagent has RMgX + MeSSMe RSMe + MeSMgX (24)
less tendency to form ate complexes (Section 2.6).
Alkylations of a number of metals were among the Primary amines may be made by the reaction of an excess
earliest reported reactions of Grignard reagents, and this of Grignard reagent with chloramine, methoxyamine, or other
reaction remains an important method for the synthesis O-substituted hydroxylamines (equation 25). Reactions with
of organometallic compounds. The alkali metal and higher N-chloroamines and N-substituted hydroxylamines are not as
alkaline earth metal cations are too electropositive to be routinely successful, because of competing displacement on
alkylated by Grignard reagents, but in principle, displacement the halogen. Displacements at PX or POR bonds are useful
at any other metal center is feasible. Since this reaction is for synthesis of trialkylphosphines. Similar displacements also
discussed in other articles as it may apply to the preparation occur with POCl3 and its derivatives. Three organic groups
of organometallic compounds of the various metals, only can be introduced in PCl5 .
general comments will be made here. A halide ion is the most
common leaving group, although OR , SR , and other anions RMgCl + H2 NOMe RNH2 (25)
may be displaced. Reactivity of R2 Mg is greater than that of
RMgX, and reactions are usually faster in THF than in diethyl Alkylation of group 14 halides is also important
ether. The center to be alkylated decreases in reactivity as synthetically. A number of reactions of R3 SnX compounds
BERYLLIUM & MAGNESIUM: ORGANOMETALLIC CHEMISTRY 13
with methyl Grignard reagents have been studied kinetically. reagents often couple in quite good yield with methyl iodide
The reactions occur with low activation enthalpies but and methyl or primary alkyl sulfates or sulfonates (i.e.
large negative entropies of activation. A cyclic four-center tosylates). Allylic and benzylic halides and -haloethers and
mechanism has been proposed to explain the results. Some -sulfides also undergo easy displacement.
alkylations, however, probably occur by single-electron Alkoxide ions are generally poor leaving groups, but
transfer (SET) from the Grignard reagent to the substrate, are displaced under special circumstances. Ring opening
followed by homolytic bond cleavages and recombinations. of the strained oxirane and oxetane rings by addition of
This mechanism is discussed in the next section in connection a Grignard reagent is such a reaction, and provides a
with displacement reactions at carbon. synthetically useful two- or three-carbon chain extension
Alkylation of a compound with multiple leaving groups (equation 28). With substituted oxiranes, the Lewis-acidic
by a di-Grignard reagent can produce a ring. Many important activity of the magnesium affects the regiochemistry of the
heterocycle and metallacycle syntheses have followed this addition, and preliminary rearrangement of the oxirane leads
route. Examples are in equations (26) and (27). to additional products.
Cl O H2O
BuMgBr + Bu
OH (28)
BrMg MgBr + Ph P P Ph
Cl Alkoxide ions may also be displaced from orthoesters
(26) and acetals (e.g. equation 29), including paraformaldehyde. A
carbocation generated from any of these structures would be
BrMg(CH2)4MgBr PPh3 Ph3P stabilized by conjugation with the adjacent lone pair (i.e. 25).
PtCl2 Pt (27) The substrate may initially form an ion pair assisted by the
Ph3P
Lewis-acidic magnesium, or at least react by a transition state
with enhanced cationic character. Grignard reagents appear
to be more effective than organolithium compounds, and the
5.5 Displacements at Carbon: Crossed Coupling lithium reagent is also more likely to deprotonate the acetal.
Reactions Leaving group reactivity is in the sequence ArO > RO >
RS > R2 N . Alkoxy groups may also be displaced from
A nucleophilic displacement by an organometallic com- propargyl and allylic ethers (often with attack at the 3-position)
pound at carbon generates a new CC bond (Scheme 2). and from the homoallylic ether (26). Under forcing conditions,
Although a general reaction, its success may be limited aryl alkyl ethers (especially methyl) are cleaved (equation 30).
because of competing side reactions. These are also outlined Another generally very poor leaving group, cyanide, is dis-
in Scheme 2. As a nucleophilic substitution, -elimination placed from -aminonitriles in a useful amine synthesis (equa-
to alkene is an important competitor, becoming progres- tion 31), and biaryls can be prepared by the (Ni-catalyzed)
sively more dominant for secondary and tertiary substrates. coupling of benzonitrile with aryl Grignard reagents.51
Metal halogen exchange, displacement by the halide of the
Grignard reagent, and radical processes resulting from SET
EtMgBr
also occur. Grignard reagents are less reactive than organo- (29)
lithium compounds and give good yields only in the more PhO OEt Et OEt
favorable situations. The partially delocalized allylic or ben- 150 C
zylic Grignard reagents are relatively effective. ArOMe + MeMgI ArOMgI + Me2 O (30)
Of the halide leaving groups, iodide is most easily Me2N CN RMgX Me2N R
displaced, but also most reactive in metal halogen exchange; (31)
R R R R
bromide and chloride are successively less reactive. Grignard
H
R + R Other products t-BuO
R
R
+
e transfer Y Y+
R R
RH + R(H) RMgX + RY R R
(25) (26)
RMgY + RX R R
+
R R
RY + RMgX A variety of mechanisms may participate in the
displacement reactions surveyed above. Some displacements,
including tosylates and some epoxide ring openings, occur
Scheme 2 with the high degrees of inversion of configuration expected
14 BERYLLIUM & MAGNESIUM: ORGANOMETALLIC CHEMISTRY
for an SN 2 reaction. As noted above, electrophilic assistance topics are also noted in other articles from the viewpoint of
by the magnesium may be important. In other cases, SET, the various transition metals.
radical formation, and recombination may be involved, as
shown in Scheme 2. A number of reactions which are formally
displacements at an unsaturated or aromatic carbon probably 5.6 Addition and Substitution at Carbonyl Carbon8,9
occur by a mechanism of addition followed by elimination of
The addition of organomagnesium reagents to aldehydes
a leaving group. As such, they are more closely related to the
and ketones, yielding an alcohol after workup, is their most
addition reactions which are covered in Section 5.8.
important organic synthetic reaction, and customarily bears
Addition of a transition metal compound can effectively
the title The Grignard Reaction. With the derivatives of
promote displacement reactions by organomagnesium com-
carboxylic acids the initial adduct may suffer loss of a leav-
pounds, often minimizing the side reactions which limit the
ing group, regenerating a new carbonyl compound, which
use of the Grignard reagent itself. Normant reagents or Grig-
in turn may undergo further addition. Scheme 3 summarizes
nard reagents with catalytic amounts of CuI salts are reactive
these processes.
in displacements of halide not only from alkyl halides but also
aryl, vinyl, and alkynyl halogen compounds. Complications
in additions to oxiranes are often reduced or eliminated. A 5.6.1 Addition to Aldehydes and Ketones8,9
number of displacements of other leaving groups are also
catalyzed by copper salts. These include RO , RS , OH , The addition of R2 Mg or RMgX to an aldehyde or ketone
and OAc groups, most commonly from allylic and propargyl is usually very rapid, occurring essentially with mixing. Only
substrates. The utility of Ni and Pd catalysts, which are with severe steric hindrance, low temperatures, or both, is
more useful with less-reactive alkenyl and aryl substrates, the reaction noticeably slow. It is generally preferred in
has been extended to aryl chlorides with the application competition with displacement of an alkyl halide or addition
of bulky, electron-rich (often phosphine-derived) ligands.52 to most other unsaturated functional groups. Reaction with
Inexpensive and nontoxic Fe catalysts are an important recent an acyl halide is usually more rapid, and a Grignard reagent
development, as they enable cross-coupling reactions that will normally abstract the OH proton (be hydrolyzed) before
are exceptionally fast even at low temperatures, and in the adding to the carbonyl of a hydroxyaldehyde or -ketone.
absence of added ligands. Mechanistic studies indicate that The alkoxide (27) is the initial product of addition to
in certain cases, inorganic Grignard reagents, of monomer the carbonyl group (Scheme 3). Workup with aqueous acid
composition Fe(MgCl)2 , are the active species, likewise able generates alcohol (28) and water-soluble magnesium salts.
to oxidatively add unactivated aryl chlorides.53,54 In reactions However, with sensitive alcohols this workup may lead to
with Cu catalysts, allylic leaving groups are usually more eas- dehydration. Milder workup can be achieved by acidifying
ily displaced than their saturated analogues, Chiral complexes with aqueous ammonium chloride, or by hydrolyzing with
have been used to achieve asymmetric cross-coupling.8 These a minimal amount of water, and attempting to filter or
H2O (workup)
RR1R2COH
R = H, alkyl, aryl,etc.
(28)
O+MgX
O O
R2MgX MgXY R2MgX
R1 R1 R R1
R = Y = OR, NR2, etc.
R R2 R2
(27) (29)
OH HY
H2O (workup)
R1 Y O+MgX
R=Y
R2
R1 R2
(31)
R2
H2O
(workup)
R1R2R2COH
(30)
Scheme 3
BERYLLIUM & MAGNESIUM: ORGANOMETALLIC CHEMISTRY 15
decant from the frequently gelatinous magnesium salts. The and a chiral ligand additive (35).56 Grignard reagents chiral at
magnesium alkoxide itself may be useful without hydrolysis the (octahedrally coordinated) metal57 (36 depicts -cis-[(p-
to the alcohol. It may be acylated by reaction with an CH3 C6 H4 )MgBr(dimethoxyethane)2 ]) or the metal-bearing
acid chloride, undergo elimination to an alkene with a carbon (20)29 are now known. The Y group in RMgY also
suitable neighboring leaving group (equation 32), or react influences the degree of stereoselectivity.58
intramolecularly as a nucleophile.
BeCl Ph
Me3Si O Me3Si O O O
RMgX H
(32)
R R N
R OMe
(32) (33)
Despite its apparent simplicity, the addition of a Grignard
reagent to an aldehyde or ketone is subject to side reactions
which may limit its utility. The transfer of a -hydrogen
from the organomagnesium compound to the carbonyl carbon
reduces the ketone to a secondary alcohol rather than
producing the expected tertiary alcohol. The alkyl group of the N
Grignard reagent becomes an alkene. This pathway is more
important with sterically hindered ketones and bulky Grignard Me N Mg
reagents. Enolization of the carbonyl compound, with the Mg N Me
organomagnesium acting as a base, is another side reaction
which is more important with substantial steric hindrance. N
Addition is promoted by lower temperatures, a less-polar
medium (Section 4.1), and by the addition of salts. A classic
comparison of normal addition, reduction, and enolization
is shown in equation (33). When electron transfer occurs (34)
between an organometallic and a carbonyl compound, ketyl
radicals are formed (see discussion below).
O
N
OMgBr OMgBr OMgBr
OH
+ + + (35)
MgBr + +
O
O O
Addition
Mg
Enolization Reduction O Br
(8%) (11%) (78%)
(33)
R1R2C OMgX
R
RMgX MgX R
R1
+ O Reduction
R1 R2 R1R2C OMgX
O (37) (38)
R2
R1R2C CR1R2
Scheme 4
alkyl and ketyl radicals of this pair can collapse to simple of the reaction depends first upon whether the initial
1,2-addition product, transfer a hydrogen atom to produce adduct (27) survives the reaction conditions, or decomposes to
reduction product, or diffuse apart. In the latter case the ketyl ketone (29). If (29) is formed before workup, then its reactivity
could either abstract hydrogen from solvent (leading also to relative to the original acyl compound determines whether it
reduction product), or dimerize to the pinacol. While early or alcohol (30) is the product.
evidence suggested that SET was a side reaction induced by
transition metal impurities, subsequent data, including that Carboxylic Acids and Carboxylate Ions. Acid base
from radical rearrangement probes, CIDNP enhancements, reaction with a Grignard reagent rapidly converts a carboxylic
and isotope effects, implied that many, or possibly all, acid into its anion. The carboxylate ion, either from a
Grignard additions to aromatic ketones involved SET, and that carboxylic acid substrate or as a preformed salt, is relatively
it may not be limited to aromatic substrates.8,9,25,59 However, unreactive, but does undergo either single addition to produce
reactions of aldehydes with the chiral (20), where the sec-alky an aldehyde or ketone or double addition to produce an alcohol.
radical functions as an ultrafast racemization probe, proceed Sometimes, as in equation (34), the carbonyl compound may
with retention of configuration, a result consistent with both be formed in good yield, but the analogous synthesis with a
a polar mechanism and a virtually instantaneous coupling of lithium reagent is more frequently used. More commonly,
ketyl and alkyl radicals.29 these products are encountered as side reactions in the
carbonation of an organomagnesium compound.
X X
Mg Mg 2PhMgBr + HCO2 H PhCHO (34)
(81%)
O C O C
C C C H Acyl Halides and Anhydrides. The carbonyl of an acyl
H C
halide is at the high end of the reactivity range, and the halide
(39) (40) ion is a very good leaving group. Hence, the reaction rapidly
forms the ketone. With one equivalent of organometallic at
low temperature, especially with some steric hindrance, the
When a carbon carbon double bond is conjugated to the
less-reactive carbonyl of the ketone may survive unreacted.
carbonyl group, simple 1,2-addition to the carbonyl has a
Otherwise, it is converted to the tertiary alcohol in high yield.
competitor in the conjugate or 1,4-addition, resulting in net
More commonly, if a ketone synthesis is sought the Grignard
addition to the carbon carbon double bond. This situation will
reagent is converted to another organometallic with attenuated
be discussed in connection with the addition to carbon carbon
reactivity. Historically, organocadmium compounds served
unsaturation (Section 5.8)
this purpose, but the currently popular choice is a Normant
reagent (a magnesium organocuprate). Manganese, zinc,
5.6.2 Substitution and Addition Reactions with Carboxylic and iron salts have also been used. Another helpful ploy
Acid Derivatives is to use HMPA as solvent; in this medium the ketone
is rapidly deprotonated to the unreactive enolate. With
The general picture in Scheme 3, with R = Y, outlines the aromatic acid halides in particular, electron transfer may
paths available when an organometallic compound reacts form the acyl radical, which dimerizes to produce an -
with a carboxylic acid derivative. The eventual product diketone.
BERYLLIUM & MAGNESIUM: ORGANOMETALLIC CHEMISTRY 17
Chloroformates, chlorocarbamates, and phosgene are against the second addition. Aldehydes, in particular, can be
similarly reactive toward organomagnesium compounds. The synthesized usefully (equation 36). Under forcing conditions
first two provide useful syntheses of esters and amides, a second addition occurs.
respectively, but phosgene usually leads to the tertiary alcohol.
Carboxylic anhydrides are similar to the halides, producing
ketones by reaction with one equivalent of organometallic, but RMgX
Me Me
easily reacting with an excess of the reagent. Cyclic anhydrides N N N N
produce lactones as final products with two equivalents of XMg R
organometallic (equation 35). O H O
H (36)
H+ H2O
O
BrMg(CH2)5MgBr H+ O
O +
OMgBr O N NHMe R H
O CO2MgBr
O
Carbon Dioxide, Isocyanates, Ketenes, etc. The carboxy-
(35) lation (or carbonation) of organomagnesium compounds is of
major importance, both as a synthesis of carboxylic acids and
Esters, Lactones, and their Sulfur Analogs. The ester as a means of characterizing the organometallic compound.
carbonyl is inherently less reactive than a ketone, so that Customarily, the organomagnesium solution is added to dry
alcohols are the normal products of addition of a Grignard ice. Under these conditions the temperature is kept low and
reagent to an ester. The reaction is useful for forming tertiary the concentration of CO2 high, minimizing further reaction
alcohols (or secondary from formates) with two R groups of the organometallic with the initially formed magnesium
identical. Cyclic alcohols may be made using di-Grignard carboxylate. If dry CO2 is bubbled through a Grignard reagent
reagents. If the organic groups are somewhat bulky, addition or passed over the solution, multiple addition is more probable
may be stopped at the ketone stage. With some lactones, (equation 37).
reaction with one equivalent of reagent is also favored
(Scheme 5). Ring strain may enhance the reactivity of the ester MgBr
group, while the cyclic hemiketal anion (41) would partially O
protect the carbonyl group of the product. CO2 OMgBr H2O
O
Similar considerations apply to thioesters and -lactones, OMgBr
OMgBr
MgBr
although they are less studied. Generally, the thioester
MgBr
carbonyl is more reactive toward nucleophiles.
(37)
O R
R R
OMgX OH
RMgX H2O O
O O O
OH
(41)
R R R R OH
O RMgX OMgX H2O OH
OH OMgX OH
Scheme 5
18 BERYLLIUM & MAGNESIUM: ORGANOMETALLIC CHEMISTRY
O O R
LiN(SiMe3)2 (1) RMgX
RCH O RCH NSiMe3 NH2
(2) H2O
Cl PhMgBr Cl R
N N
Scheme 6
C
Ph OMgBr
O (39)
R R
NH O
H2O R R
R H+
RMgX
RC N NMgX
R R R
RMgX H2O
R N(MgX)2 R NH2
R R
Scheme 7
BERYLLIUM & MAGNESIUM: ORGANOMETALLIC CHEMISTRY 19
5.7.2 Addition and Substitution to Carbon Phosphorus is a powerful ring synthesis method.
Unsaturation
MgX
1,3,5-triphosphabenzene initially undergoes 1,4 addition
with Grignard reagents (the R group of the Grignard adds to MgX
phosphorus) to ultimately yield unusual diorganomagnesium C6H13
salts containing a Mg(THF)6 dication, and C3 (t-Bu)3 P2 P
anions bearing a partially delocalized charge (equation 42).60 C6H13 (43)
MgX
The phosphaalkyne PC(t-Bu) adds RMgCl to yield the MgX
phosphavinyl Grignard reagent RP=C(t-Bu)MgCl, which +
C6H13 C6H13 MgX
crystallizes as the chloride-bridged dimer.61 The polarity of
addition (MgX bound to carbon) is opposite to that observed
for nitriles. 15 : 85
t-Bu
+
P P
Mg
CH2
MgX X
t-Bu P t-Bu
(44)
RMgX
THF
(42)
ClMg
H2O
+ MgCl
MgX
RMgX
Me3Si Me3Si
R
MgX
RMgX
RFCF2 RFCF2 RFCF
R R
Scheme 8
BrMg
Cp2Ti (50) (42)
TiCp 2 MgCl
n-BuMgCl
R R With 1,3-dihalides, elimination to produce a cyclopropane
Cp2TiBu
can be a problem. Elimination predominates strongly when
the halogens are on adjacent carbons. Aromatic ortho di-
Grignard reagents and that from 1,2-dibromocyclopropane
5.9 Other Reactions may be formed because the competing elimination yields a
more strained system. BrMgCH2 CH2 MgBr has been made
A number of reactions which did not to fit neatly into the from LiCH2 CH2 Li and MgBr2 .
foregoing categories are shown in Scheme 10. A number of 1,1-di-Grignard reagents have been reported,
including CH2 (MgX)2 (X = Br, I, from the dihalide and
R R
Mg/Hg), and (43). Pyrolyzes of Me2 Mg and Me2 Be produce
R HO
RMgX E 2 polymeric (MCH2 ).
RN C RN RN O
MgX E E
BrMg MgBr
E= H+, CO2, RX
S SR
SR Me3Si SiMe3
RMgX RMgX
MgX (43)
R R R
R R R
75150 C Mg
RMgX + H2 RH + MgX2 + MgH2 + Cp2TiCl 2 TiCp 2
340 atm (51)
Scheme 10 4
22 BERYLLIUM & MAGNESIUM: ORGANOMETALLIC CHEMISTRY
The structures of dimagnesium compounds are also of generally eliminated so readily that no Grignard reagent
interest. With an ,-di-Grignard reagent the R2 Mg species can be detected. However, Grignard reagents with -
in the Schlenk equilibrium can be a magnesiacycle. The cyclic amino groups have been obtained at low temperature,
dimer structure in equation (52) has been confirmed by X-ray and perfluoroalkyl Grignard reagents have limited stability.
crystallography. Halide-free organomagnesium compounds o-Haloaryl Grignard reagents can also be formed, but
from 1,2-dihalobenzene, 1,8-dihalonaphthalene, and 1,2- these compounds decompose to generate benzyne. Some
dihalo-1,2-diphenylethylene have unique tetrameric cluster organomagnesium compounds with -halogen can be formed
structures with 3 bridging organic ligands and a tetrahedral at low temperature (equation 13), but decompose on warming,
arrangement of magnesiums.9 either via free carbenes or to carbene-derived products.
Grignard reagents ROCH2 MgX decompose above 15 C to
ethylene and ROMgX. R3 Si and R3 Sn may be in , , or more
BrMg MgBr Mg + MgBr2 distant positions.
Br Mg MgBr
Y Y C2H4 + MgYBr
(53)
(THF)2Mg Mg(THF)2
MgCl
Me2
ClMg MgCl Si O MgBr
BrMg N
ClMg MgCl Si BrMgO
Ru Me2
ClMg MgCl (46)
(45)
221 223 pm; CMgC = 78 79 ). With anthracene and flow tube studies, the reactivity of Mg+ , CpMg+ , and
1,10-dimethylanthracene the magnesium was coordinated to Cp2 Mg+ ions with small inorganic molecules and straight
three THF molecules and was further (232 pm) from the chain hydrocarbons has been probed. CpMg+ was the most
carbons, suggesting a more ionic interaction. Magnesium reactive of the three ions.70 Magnesocenes with substituted
anthracene compounds serve as active carriers for mag- cyclopentadienyl ligands, including rings bearing methyl,
nesium atoms, and decompose to deposit a very active trimethylsilyl, tert-butyl, and methoxy substituents are known.
finely divided magnesium. Silica and polymer supported The recently determined solid-state structure of Mg(C5 Me5 )2
Mg anthracene complexes offer certain advantages over reveals the presence of both staggered and completely
Mg (anthracene)(THF)3 in the preparation of Grignard disordered conformers.71 The substituted-ring species form
reagents. stable adducts with N-heterocyclic carbenes.72
THF THF
Mg R Be Be (54)
R
(47) Dicyclopentadienylberyllium10 has a substantial dipole
moment, indicating an unsymmetrical structure. A variety of
structures have been proposed, based on different experimental
Conjugated dienes also react with magnesium in THF8 data. The molecule adopts a slip-sandwich structure in
(usually with some activation). With 1,3-butadiene the the solid and vapor, with the Be atom disordered equally
initial product is THF-solvated [C4 H6 Mg], which can over two sites, and the two rings 5 and 1 bonded.
add more butadiene molecules. The 1:1 and 1:2 adducts Equation (54) depicts the Be atom disorder in the solid-state
are reasonably formulated as allylic organomagnesium structure. The metal ligand bonding is relatively weak: a
compounds (48) or (49). These complexes are diamagnetic, sharp singlet is observed in the 1 H NMR down to 135 C,
hydrolyze to alkenes with incorporation of two D atoms from indicating rapid averaging of the environments of the two
D2 O, and undergo reactions typical of Grignard reagents. rings. Molecular dynamics calculations credit two ultrafast
Net 1,2- or 2,1-addition can be effected, depending on (activation energies of less than 10 kJ mol1 ) processes, a 1,5
the nature of the electrophiles. Electrophiles with two sigmatropic shift of the Be(5 -C5 H5 ) unit around the periphery
electrophilic centers can lead to carbocyles, including spiro of the 1 - ring (depicted in Scheme 11 for Be(C5 Me4 H)2 ),
compounds.8,9 and a ring/molecular inversion that interchanges the 5
and 1 rings (Scheme 12), for the isomerization.73 BeCpX
complexes (X = H, Cl, Br, Me, CCH, C5 Me5 , BH4 , B3 H8 ,
Mg B5 H10 , and SiMe3 (Section 6.7)) appear to be monomeric
Mg
in all phases, with C5 H5 (centroid)Be distances, where
n
determined, similar to that of the 5 -bonded ring in Be(C5 H5 )2
(48) (49)
(147 pm). X-ray diffraction reveals that while the octa-
and nonamethylberyllocene derivatives (C5 Me4 H)2 Be and
(C5 Me4 H)Be(C5 Me5 ) exhibit slip-sandwich 5 /1 structures
6.4 Cyclopentadienyl Compounds69
(where the 1 ring bonds Be via the secondary, i.e CH
carbon), the deca methyl derivative Be(C5 Me5 )2 adopts
Crystalline dicyclopentadienylmagnesium3,12 has a
a ferrocene-type 5 /5 structure with parallel rings.74
monomeric sandwich structure, with the rings staggered.
Insertion of an isocyanide into the Be1 (C5 Me4 H)
Its long ring metal distance, along with vibrational and
bond of (C5 Me4 H)Be(C5 Me5 ) yields two different iminoacyl
photoelectron spectroscopic data, imply ionic character, but
isomers (Scheme 13). As these isomers correspond to those
other experimental (e.g. 25 Mg NMR) as well as theoretical
depicted in Structure 11, they constitute chemical evidence
studies suggest significant covalent binding.35,69 Addition of
for the proposed isomerization mechanism. Half-sandwich
HMPA to an ether solution leads to solvent-separated ions.
compounds (C5 Me5 )BeX, where X = Cl, Br, P(t-Bu2 ), As(t-
Mg(C5 H5 )2 forms adducts with many Lewis bases, and is
Bu2 ), Me, t-Bu, CH2 CMe3 , and CH2 Ph have been prepared.75
a useful reagent for the transfer of C5 H5 groups. Mono -
(C5 H5 )Mg complexes, that is, CpMgX, are generally isolable
only as base adducts. The TMEDA adduct of CpMgBr and 6.5 Allylic and Benzylic Organomagnesium Compounds
the dimer [CpMgMe(Et2 O)]2 have the ring bonded nearly
symmetrically to the metal and distorted tetrahedral metal Allylmagnesium compounds appear to undergo a rapid
geometry; the latter has bridging methyls. In selected ion allylic shift of the magnesium between the two methylene
24 BERYLLIUM & MAGNESIUM: ORGANOMETALLIC CHEMISTRY
H H H
Be Be Be
H H
H
Scheme 11
isomers.76
MgBr BrMg
Be Be Be (55)
H
H C H
Scheme 12 C C
H Mg H
X
termini of the allyl group (equation 55). An alternative
description is an allyl group symmetrically bonded to the (50)
magnesium, either covalently bridging 3 as depicted in
(50) or as an ion pair. Early NMR and IR data could not Alkyl substitution (equation 56) destabilizes the allylic
distinguish between these alternatives. More recent, higher isomer (51) with the more highly substituted -carbon, so that
field 1 H and 13 C NMR spectra are likewise ambiguous, in it is not detected directly in the equilibrium mixture. However,
that low-temperature spectra exhibit extreme broadening as cis trans isomerization, rapid on the NMR timescale even
opposed to separate methylene resonances. IR spectra of at low temperature, likely occurs via rotation about the
1,1- or 3,3-dideuterated allymagnesium bromide solutions single bond in the low equilibrium concentration of (51).
reveal, however, a pair of bands due to the C=C bond stretch, The position of equilibrium has been deduced from 1 H NMR
consistent with the rapid equilibration of unsymmetrical allylic coupling constants; with R = Me, the (Z)-isomer is favored
Be
C
N
H
H
25 C 25 C
H
+ C N
Be
H 78 C Be
C H
N
Scheme 13
BERYLLIUM & MAGNESIUM: ORGANOMETALLIC CHEMISTRY 25
MgX R
(51) (C5H5)Be(SiMe3) SiMe2
(56)
Be + Be
R MgX Me SiMe2SiMe3
50. B. A. Trofimov and S. E. Korostova, Russ. Chem. Rev. (Engl. 70. R. K. Milburn, M. V. Frash, A. C. Hopkinson, and
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Biomineralization Abbreviations
200 m 200 m
(d)
2.5 cm
(b) (f) (g)
2 cm 1 cm 1mm
5 mm (c)
(a)
0.5 cm (h)
(e)
Figure 1 Some examples of mineralized skeletons: (a) Longitudinal section in a mineralizing sponge. (b) Zooids in Bryozoa. (c) Shell of a
scaphopod (Mollusks). (d) Ornate shell of an Ostracod (Arthropoda). (e) The coiled shell of Spirula (Mollusks, Cephalopods). (f ) Apical view
of a sea urchin. (g) Fish otolith. (h) Teeth and bone of a small Mammal
10 m 1 mm
Figure 2 Scanning electron micrographs of biosilica. (a) Ornate morphology of a frustule of a diatom. (b) Ornate test of a radiolaria. (c) A
siliceous sponge (Euplectella) showing the highly organized spicule framework. (d) Transverse section of a giant spicule showing a concentric
growing pattern (Monoraphis)
phytoliths). Diatom exoskeletons (=frustules) are composed Nevertheless, this common name conceals a large variety of
of globular particles and consist of colloidal aggregates.2 structures and compositions.
Sponges use specialized cells called sclerocytes to synthesize
silica spicules, and the shape and arrangement of the spicules
depend on the species (Figure 2(c)). The process of extrusion 2.2.1 Bone
of the spicules is yet poorly understood, but the presence
of an axial filament containing proteins suggests they are Bone is a true biological tissue, since it contains cells,
and is continuously forming and reforming. Different levels
involved in the formation of the mineral (Figure 2(d)). The
of organization have been described, following the progress
transverse section of a spicule shows regular growth lines and
of microscopes. Adult bone is of two basic architectural,
an annular organization of nanoparticles of about 70 nm in
macroscopic types: compact or cortical, and cancellous or
diameter.3
spongy, but there is no sharp boundary between them. In
In diatoms (unicellular algae), silica is a composite material
compact bone, most of the individual lamellae form concentric
containing glycoproteins. The walls are almost pure hydrated
lamellae around longitudinal canals (50 m in diameter) within
silica with small amounts of Al and Fe.
the bone tissue. These canals typically run parallel to the
surface and along the long axis of the bone. The canals and
the surrounding lamellae are called a Haversian system or
2.2 Phosphates an osteon (Figure 3(a)). The cortical and trabecular bones
have a hierarchical structure with three or four lower levels.
The main part of the calcium phosphate minerals Various models of the plywood structure have been described
produced by organisms is crystalline and described as apatite. (Figure 3(b), (c)).46 The basic level of organization is the
BIOMINERALIZATION 3
Figure 3 Structures of mammal bone: (a) Haversian systems and osteons. (b) Plywood-like structure with twisted lamella. (c) Lamellar
bone showing the different orientations of fibers in successive lamella. (d) Mineralized collagen fibers
Absorbance
Amide II
probably the smallest biocrystals with average dimensions of
Amide I
50 25 5 nm.
The mineral fraction of bone is usually called hydroxy- CO3
lapatite, carbonated hydroxylapatite, or dahllite. However, n3
bone apatite contains carbonate ions but lacks hydroxyl ions.
Polarized light and X-ray diffraction studies have shown that
Amide A
PO4
the bone crystal c axes are aligned with the collagen fiber n1
axis. The organo-mineral composition of the bone is clearly n3
n4
shown by infrared spectra (Figure 4). The average chemi- PO4
cal composition of mammal bone is illustrated in Figure 5.
Na and Mg are mostly associated to the mineral fraction,
but S is probably mainly associated with sulfated polysac- 4000 3000 2000 1000 cm1
charides of the organic matrix. In modern mammals, it has
been shown that some elements are sensitive to diet or preg-
nancy (Sr). The major organic component of bone is type Figure 4 Infrared spectra showing the dual composition of bone
with organic (amide) and mineral bands
I collagen, and the noncollagenous proteins or NCP con-
tain more than 200 proteins. Four main groups of NCPs are
found: proteoglycans, -carboxylated (gla)-proteins, glyco- be divided into intertubular and peritubular dentine. The
proteins, and others. Chondroitin sulfate, heparan sulfate, peritubular dentine forms a hypermineralized sheath around
and keratan-sulfate are present in the side chains of pro- the dentinal tubule. The plate-like structures of the apatite
teoglycans. Almost the entire mineral is found within the crystals of the intertubular dentine have their c-axes parallel
collagen fibers. The banding pattern of the collagen is to the long axes of the collagen fibrils.
about 70 nm. The alignment of small plates, the thickness In human teeth, the mineral fraction constitutes about 70%
of which is about 65 or 140 nm may reflect the collagen matrix of the dentine by weight, and about 50% by volume. The aver-
(Figure 3(d)). age chemical composition is similar to that of bone (Figures 5,
7); however, due to the high Mg contents of ever-growing
teeth in mammals (i.e. incisors in rodents and lagomorphs),
2.2.2 Dentine (=Ivory)
the profiles are not identical. Sr contents are also different
Dentine structure and chemistry vary between different (Figures 5, 7). Ca/P ratio (by weight) is lower than that of
species. For example, the rodent incisor is an ever growing bone. As in bone, the fibrous collagen I constitutes about 90%
tooth, and thus differs in the basis of dentine formation from of the organic matrix. The intertubular dentine composition is
that of the human tooth. very similar to that of bones, and consists of a fibrous network
In reptile teeth, under the external thin enamel layer, the of collagen with deposited mineral crystals. The reported max-
dentine shows numerous regular growth lines (Figure 6(a)). imum differences in the mineral content between peritubular
Dentine has a highly organized structure, and in reptile and and intertubular dentines vary from 9% to 40%.8 The peritubu-
mammal teeth has an array of parallel pores or tubules lar dentine has high P, Ca, and Mg contents, but contradictory
extending from the central pulp cavity to the dentine enamel results are reported about the presence of collagen. In horse
boundary. It is called orthodentine (Figure 6(b) (d)). The teeth, the peritubular organic matrix is less abundant than the
average diameter of tubules is about 2 m. Many other intertubular matrix, both being mainly composed of collagen.9
varieties have been described in the fish scales and dermal In human teeth, the organization of the crystals of peritubular
armors of fossil vertebrates.7 In some taxa, the dentine may dentine is very similar to that of the adjacent intertubular
4 BIOMINERALIZATION
ppm 2
Bone
12000
Ca/P
Dentine
1.5
Enamel
8000
1
4000
0.5
0 0
Na Mg S K Mn Fe Sr Cl Bone Dentine Enamel
Figure 5 Chemical composition of mammal bone, dentine and enamel, and Ca/P weight ratios
200 m E
Figure 6 Structure of dentine: (a) Polished and etched longitudinal section of a crocodilian tooth, showing the thin outer enamel layer (E) and
the growth lines in the inner dentine (D). (b) Oblique section of orthodentine showing the tubules. (c) Oblique section of the orthodentine
of a small mammal incisor showing the tubules. (d) Transverse section of the orthodentine of a small mammal tooth showing empty and
filled tubules
ppm ppm
Incisors
Dentine Incisors Enamel Non incisors
Non incisors
6000
8000
4000
4000
2000
0 0
Na Mg S K Mn Fe Sr Cl Na Mg S K Mn Fe Sr Cl
(a) (b )
Figure 7 Chemical composition of rodent teeth: (a) Dentine, showing the difference in Mg contents between the ever-growing incisors and
the other teeth. (b) Enamel, with no Mg difference between the ever-growing incisors and the brachyodont teeth
dentine. In human intertubular dentine, the apatite crystals are 2.2.3 Enameloid Enamel
closely associated with the collagen matrix. The main protein
in peritubular dentine has a higher molecular weight and a dif- Enameloid and enamel compose the outer layer of teeth, and
ferent aminoacid composition than the phosphophoryns of the both are usually described as hypermineralized tissues, despite
intertubular dentine. Both dentines are in structural continuity. the fact that they differ in their structure, composition, and
BIOMINERALIZATION 5
Figure 8 Structure of enameloid and enamel: (a) Ganoine, with incremental lines (arrows) in a fossil fish tooth. (b) Acrodin, with a complex
structure, in a fossil fish tooth. (c) Complex and regular pattern of the prismatic enamel in a rodent incisor. (d) Another prismatic pattern in
a rodent incisor. (e) Nonprismatic enamel in a polished and etched crocodilian tooth showing growth lines (arrows). D: dentine; E: enamel.
(f ) Alligator mississippiensis: elongated and parallel enamel rods. (g) Polished and etched section of a tooth of Crocodylus niloticus, showing
parallel long rods with aggregates and layers of organic material (arrows). Atomic Force Microscopy (AFM) Phase image. (h) Detail of the
same; arrows: layers of organic material
formation. Enameloid is the enamel of fishes (Figure 8(a)), glycoconjugates, whereas in the mammal prismatic enamel
but there is a confusing variety of names (enamel, enameloid, sulfated glycoconjugates are detected preferentially in the
collar ganoine, etc.), all of which lack adequate chemical or surface layer.12
structural definitions. Another structure type present in fish
teeth has been described: acrodin is composed of interwoven
fibers (Figure 8(b)).10 The main part of the enamel of mammal 2.3 Carbonates
teeth is organized in prisms or rods. A prism is composed
of parallel acicular crystals of enamel, and the arrangements 2.3.1 Structure
of the prisms are variable (Figure 8(c), (d)). The tooth enamel
has the most unusual morphology of the apatite biocrystals: Calcium carbonate minerals (CaCO3 ) are ubiquitous in
mature enamel contains crystals that are tens of microns long biomineralizing systems, since they are in the skeletons
with an aspect ratio (length/width) of at least 1000. The of organisms ranging from bacteria and algae to humans,
reptilian enamel is usually without prisms (Figure 8(e)), and most commonly as calcite (rhomboedral) or aragonite
is composed of parallel acicular crystals (Figure 8(f ), (g)). (orthorhombic). Thus, their structures and compositions are
In recent crocodile teeth, waves of an organic matrix are highly diversified. Here, only some examples are discussed.
present between the crystals (Figure 8(g), (h)). Their shape The most studied taxa is the Mollusks, since the pioneering
and location are similar to the small droplets and the rows of work of Boggild on the microstructure and mineralogy of
nanospheres of amelogenins observed in mammal enamel.11 modern and fossil shells.13 Mollusk shells are composed of
The tooth enamel has the most unusual morphology of calcite and/or aragonite, usually separated in different layers.
the carbonate-apatite (dahllite) crystals. In mature enamel, the Boggild has classified the structures, has shown that the
mineral part may reach 98% by weight (=90% by volume). mollusk shell is layered, and that the spatial distribution of
Mammal enamel has a low Mg and S content compared with the shell layers is characteristic of the taxa at the genus-
the bone and dentine (Figure 5). There is no difference in Mg species level. Moreover, these structures are characteristic of
contents of ever growing and brachyodont teeth (Figures 5, Mollusks and are not found in other taxa. Of these layers,
7). The low S content is probably related to the low organic the best known, but not the most common, is the nacreous
contents of the tissue. Unlike bone, the enamel organic matrix layer (Figure 9). The wall of bricks where bricks are mineral
does not contain collagen. Enameloid is usually rich in F. There tablets, and mortar is interlamellar and intercrystalline organic
are distinct differences in the composition and distribution membranes, is a common feature of the nacre (Figure 9(a)).
of sulfated glycoconjugates in enameloid and enamel. The However, the shapes and vertical arrangements of the nacreous
fish enameloid contains chondroitin sulfate associated with tablets are different in the Cephalopoda and Gastropoda
collagen fibrils. The reptile aprismatic enamel has no sulfated on one hand (Figure 9(b)), and the Bivalvia on the other
6 BIOMINERALIZATION
Figure 9 Structure of the aragonitic nacreous layer (mother-of-pearl) in mollusc shells: (a) Typical tablets in Nautilus shell (Cephalopod).
(b) Vertical section showing the pseudoprismatic pattern of the nacreous layer in Cephalopods and Gastropods.(c) Vertical section showing
the lenticular pattern in Bivalves.(d) Tangential section showing the nonsuperposition of the successive tablets in Bivalves and the resulting
spiral pattern.(e) Detail of the structure of a tablet of Pinna (Bivalve) showing the twin and symmetrical more or less soluble sectors after an
enzymatic etching. (f ) Tangential section showing the superposition and the hexagonal shape of the successive tablets in a cephalopod shell.
(g) Etched tablet of a cephalopod shell showing the central hole and the radial sectors. (h) Rounded granules in a tablet of Nautilus. Each
granule is surrounded with a thin layer, probably composed of organic materials
hand (Figure 9(c), (d)).14 This taxonomic dependence and the organic wall varies from 1 to 8 m. Nevertheless, repeated
different growth modes in the two sets were confirmed.15 observations have shown some differences between the two
Using elaborate preparative processes, Mutvei has shown shells. In Pinctada, thin sections observed in polarized
that the inner structures (= ultrastructures) of the tablets are light show that each prism extinguishes in several smaller
different in the three main classes of Mollusks: Bivalvia blocks, whereas the individual prism of Pinna exhibits
(Figure 9(e)), Gastropoda, and Cephalopoda (Figure 9(f ), a monocrystalline extinction.13,19,20 Untreated fractures of
(g)).16 Again, the ultrastructures in the two sister groups Pinna show long straight parallel prisms with a more
(Gastropoda and Cephalopoda) are more similar than that of or less smooth surface (Figure 10(a)). Occasionally, the
the Bivalvia. The ultrastructures, now called nanostructures, surface shows a transverse lineation (Figure 10(b)). Etched
are not yet well known and only some samples have been transverse sections show the thick organic interprismatic
walls and the polygonal shape of the prisms (diameter
studied. However, the acicular crystallites of the nacreous
70 m) (Figure 10(c)). These prisms are composite units:
tablets of cephalopod shells are composed of granules
on longitudinal sections, transverse synchronous growth lines
(diameter about 40 50 nm), surrounded with a thin organic
cross the adjacent prisms (Figure 10(d)). They are composed
envelope (Figure 9(h)). The arrangement of the granules
of aligned oblique and elongated crystallites, the width of
seems dependent on the taxa. Thus, from this example, it
which varies from 150 to 180 nm (Figure 10(e), (f )). These
appears that the structures, the spatial distribution, and the crystallites are subdivided into smaller rounded units with
ultrastructures are strongly dependant on the taxonomy of the distinct boundaries, suggesting that they are surrounded
organisms, that is, the organisms fully control the minerals by organic envelopes. The etched longitudinal sections of
they produce. Pinctada also show transverse growth lines (Figure 10(g)).
Another example is given by the calcitic prismatic layer Nevertheless, in transverse sections, enzymatic hydrolyzes
of Pteriomorphid bivalves (Figure 10). The remarkable form reveal intraprismatic sinuous lacunae that are the remains
and size of these crystals have been recognized for many of intraprismatic organic membranes (Figure 10(h)). The
years.17 According to Taylor et al., the prisms of Pinna orientations of crystallites on both sides of these intraprismatic
and Pinctada are similar and called simple prisms: simple membranes within a prism are not similar.
prisms are aragonitic or calcitic, their crystallographic c axes Despite their monocrystalline habit, the nacreous tablets
normal to the layer surfaces, with each prism separated by and the prismatic units of Mollusks shells are composite struc-
a thick conchiolin wall.18 Calcitic prisms have transverse tures. We do note that these complex structures are rarely visi-
striations, whereas aragonitic prisms have longitudinal and ble on simple fractures of the shells, but enzymatic hydrolyzes
fewer developed transverse striations. The thickness of the or/and acidic etchings are effective from this point of view.
BIOMINERALIZATION 7
100 m
(e) 250 nm (f) 100 nm (g) (h) 100 m
Figure 10 Structure of the outer calcitic prismatic layers of two Bivalve shells: (a) Fracture showing the parallel and straight prisms in
Pinna. (b) Detail of the same, showing fragments of the interprismatic organic wall and a transverse growth striation in Pinna. (c) Etched
transverse section showing the hexagonal shape of the prisms and the thick interprismatic organic wall. Pinna. (d) Polished and etched section
showing the synchronous transverse growth lines. Pinna. (e) Fixed and etched polished transverse section of a prism of Pinna, showing the
regular alignment of crystallites. (f ) Fixed and etched prism of Pinna, showing the regular arrangement of the longitudinal face. (g) Enzymatic
hydrolysis of a fracture of the prisms of Pinctada, showing the thin transverse growth lines. (h) Transverse section of the same sample,
showing the preserved organic interprismatic wall and the inner prismatic membranes destroyed by the enzymatic hydrolysis
Figure 11 Spongy stereom of Echinoderms: (a) Sea urchin plate showing the various stages of the spongy stereom. (b) Starfish: in this
article, the stereom is less regular. (c) Ophiurid vertebrae. The whole structure is a single crystal of calcite. (d) Conchoidal fracture of a sea
urchin spine
Opposite to the mineralogical and structural varieties of the in minor and trace elements are strongly dependent on the
mollusk shells are the echinoderm skeletons. All of them show taxa. Many skeletons are composed of Mg calcite, with Mg
the same microstructural pattern: a calcitic spongy stereom contents greater than 10 mol% (the maximum content of
(Figure 11(a) (c)). Urchin spines and plates are composed thermodynamically stable magnesium calcite) and some as
of one single crystal of calcite, according to polarized light high as 40 mol%.21 Echinoderm tests are composed of high
and X-ray diffraction. However, the fracture surfaces are con- Mg calcite, whereas mollusk shells have low Mg calcite shells;
choidal and do not show the cleavage planes of inorganic brachiopod shell Mg contents are between them.22,23 Chemical
calcite (Figure 11(d)). contents of aragonitic sponge, coral, and mollusk skeletons
are also easily recognized with their Mg, Sr, and S contents
(Figure 12(a)). The Sr/Mg substitution ratio or L coefficient
2.3.2 Composition is discriminant for the sedimentary aragonite, sponges, and
corals and mollusk shells (Figure 12(b)).24 Within a single
The organisms strongly control not only the shapes of taxa, within a single mineralogy, some chemical element
the biominerals, but also their chemical compositions. Within contents differ. The coral skeleton is aragonitic, and composed
an uniform mineralogy (calcite or aragonite), the contents of two parts: the centers of calcification and the fibers
8 BIOMINERALIZATION
ppm L
Sponges
8000
Scleractinia 3
Cephalopods
6000
2
4000
1
2000
Figure 12 Chemical composition of biogenic aragonites: (a) Chemical composition of the biogenic aragonite of three taxa, showing the
strong differences in Sr, Mg, and S contents. (b) Sr/Mg substitution ratio or L coefficient in the three taxa
Figure 13 Structure of the Scleractinia skeletons: (a) Septal growing zone showing the centers of calcification. Diploastrea. (b) Polished
and etched section showing the median line of centers of calcification and the outer fibrous layer. Diploastrea. (c) Detail of centers of
calcification with their granular structure, and the growth lines in the fibers. Polished and etched section. Lobophyllia. (d) Polished and etched
section showing the regular growth lines. Platygyra
ppm ppm
Mg S
2000
3000
1500
2000
1000
1000
500
0 0
a a s
llia hyllia cera mia Favi mia helia racis strea uss ia a
ng por orite hyll
ia llia yllia cera mia avia mia helia racis trea ussa ngia pora rites yllia
hy ylla illo P ymp hy F
op op lad sam
o
ps
am Lop Mad onta M op oph ado am am Lop Mad ontas M o
ylla illo P ymp
h
lan Cary C allop o M Ph Poc S lan Cary Cl llops ps Ph Poc
B a
Le
p t B a a pto M S
En E n L e
Centers Fibers
Figure 14 Chemical composition of the centers and fibers in various Scleractinia species
(Figure 13). It has been shown that the centers of calcification samples, whereas XANES spectra and electrophoretic data
are the first zones to mineralize in the septa.25 According have shown that S is associated with acidic sulfated sugars.27
to the species, Mg, Sr, and S contents are significantly Similar results have been obtained in some Mollusk shells,
different in the centers and fibers (Figure 14).26 Raman and in which the main component of S is related to organic
XANES spectra have shown the absence of CaSO4 in these sulfates.28
BIOMINERALIZATION 9
3 m 4 m
(a) (b) (c) (d)
Figure 15 Qualitative chemical maps of the calcitic prisms of Pinna (1 3) and Pinctada (4): (a), (b) Electron probe maps showing the
difference in the zonation in Mg and S, and the high S content of the organic interprismatic walls (C.T. Williams, Department of mineralogy,
NHM, London); Pinna: average S content 5600 ppm, average Mg content 4600 ppm. Pinctada: average S content 3100 ppm, average Mg
content 5800 ppm. (d) Organic sulfate map showing the low content of the interprismatic wall and the high content of the intraprismatic matrix.
A growth zonation is also visible (M. Salome, ID21, ESRF, Grenoble)
A growth zonation is usually observed in mineralized Lowenstam and Weiner.1 In the biologically induced min-
skeletons. Different chemical mappings show that this eralization, an organism modifies its local microenvironment
zonation is also compositional. Electron probe maps of Mg to create conditions suitable for the chemical precipitation
and S of longitudinal sections of the calcitic prismatic layer of extracellular mineral phases. It is the dominant process in
of Pinna clearly show the organic composition of the thick fungi and bacteria.
walls, lacking Mg and rich in S (Figure 15(a), (b)). It must The second mode is called biologically controlled or
be noted that the inner part of the prisms show in both organic-matrix-mediated biomineralization, in which in-
maps a different growth zonation. SO4 maps of the prisms organic particles are grown within or on some organic matrix
show that the interprismatic wall has a low sulfate content produced by the organism. It is the process in sponges,
(Figure 15(c)), whereas the inner part has a high sulfate corals, echinoderms, and so on, in which the mineral units
content. Moreover, there is a sulfate growth zonation. Similar are aligned in a preferred direction. The unique structure and
results were obtained on Pinctada prisms (Figure 15(d)). As orientation of crystals, the morphology, and composition of
for Scleractinia, sulfate is associated with the sugars of the these biominerals are clear indications that the processes of
organic matrix.28,29 crystal nucleation and growth are highly controlled by the
Most shells or exoskeletons are made of crystalline organisms. Organisms use macromolecules such as proteins
minerals, but amorphous calcium carbonate (ACC) is also and glycoproteins to control these molecular processes.
present. These biological ACC contain significant amounts of
Mg, P and rich glutamic acid proteins.30
3.1 Silica
Mollusk shells are much tougher than inorganic calcium
carbonate minerals, and it is still unclear exactly how the Biosilicate formation occurs at ambient temperature.
growth of these structures is controlled. It is known that Biosilicates grow in closed spaces, and the organic com-
the organic macromolecules released by the dissolution of ponents influence the size and the shape of skeletal parts.
biocrystals are key participants in the control processes of In diatoms, the valve formation occurs within the cell.
shape and structure in mineralized tissues. But chemical However, the mature mineralized wall is outside the cell.
elements also regulate the biomineral properties and During the first stages of the cell wall development, small
formation rates, and provide critical information on crystal vesicles fuse to form the deposition silica vesicle, delimited
growth history. The influences of biological processes on by a membrane (silicalemna). This membrane is probably
the elemental composition of biominerals, called vital integrated in the diatom wall in the adult diatom. The mature
effects, seriously impede efforts to unambiguously interpret diatom wall is composed of amorphous silica, but different
biogenic mineral compositions in terms of environmental forms of silica have been observed at different stages of
reconstruction. growth: fibrils, spheres, hexagonal columns.30 The transport
form of intracellular Si is still very poorly understood.
Silaffins (polycationic peptides), silicateins and frustulins
have been identified as constituents of biosilica. In sponges,
3 MODES OF BIOMINERALIZATION a protein (silicatein) is probably implied in the mineralizing
process.31 Silaffins are strongly basic low-molecular weight
polypeptides. In vitro, silica formation at a pH > 7 is a very
Biomineralization involves the formation of minerals by slow process. However, in diatoms the same process takes less
organisms, and two different modes are summarized by than one hour.
10 BIOMINERALIZATION
3.2 Phosphates result of the secretion of a mantle cell. Crystals are generally
formed in predefined closed spaces, delimited by extracellular
The three main structural tissues of vertebrates, bone, macromolecular matrices. Again, the nacreous layer of the
dentine, and enamel, have different origin and behavior during mollusk shell is the structure from which some models have
the growth of the animal. Most teeth do not change once they been elaborated.
are erupted, whereas the bone is continuously modified. Transmission electron microscope studies have shown that
From a biological point of view, bone is a true tissue the organic interlamellar membranes have a lamellar structure
because it contains cells. Specialized cells are responsible (Figure 16(a), (b)).32,33 This structure varies according to
for the replacement of preexisting bone, or remodeling, that the taxa. Some fenestrations or holes have been described,
takes place both in compact and trabecular bone. Bone and they have been considered to favor the passage of
remodeling involves the dual processes of bone resorption fluid substances needed for the mineralizing process. The
and redeposition. From TEM observations, it appears that the decalcification process of the nacreous layer, and later
first step of formation is an ionic adsorption on a substrate, all the mollusc layers and invertebrate tests, has shown
leading to nanoparticle nucleation. The size and orientation of
the nanoparticles depend on the substrate.
Dentine is the first calcified tissue to be deposited Mineral tablet
during tooth embryogenesis by the odontoblasts lining the
Interlamellar
inner pulp chamber. Odontoblasts lay down the dentinal membrane
organic matrix, and the dentine formation proceeds inwards.
The mineralization begins when an organic layer of about Intercrystalline
10 20 m thick was deposited, and only cells process encased membrane
(a)
in the dentinal tubules are present in dentine.
Interlamellar
Enameloid and enamel have different structures and membrane
compositions, and differ in their genesis: enameloid is
produced by both odontoblasts and inner dental epithelial Chitin core
cells; it is deposited before true dentine is formed, and Acidic
usually includes collagen, epithelial derived proteins, and molecules
(b)
chondroitin sulfate; enamel is produced by ameloblasts after
dentine was deposited; it grows centrifugally, and contains
ectoderm-derived proteins (amelogenins and enamelins) but Mineral
Acidic
no collagen proteins. These components are almost fully macromolecules
removed throughout the maturation stage. Amelogenins,
secreted by the ameloblasts, are believed to function as the
scaffold for the initiation and growth of apatite crystals. b-chitin
Amelogenin molecules self assemble to generate nanosphere Silk fibroin-like
proteins
structures of 1 20 nm in diameter.11
In mammals, the eruption of the tooth occurs after the
Mineral
crown is formed, but the tooth gradually moves toward the
surface during its development. Nevertheless, all the teeth (c)
are not similar and three categories can be recognized.
Mammals that feed on abrasive substances have especially
high-crowned teeth. These teeth are called hypsodont. The
teeth of cows and deer are hypsodont. In some species, Asp-rich
hypsodont teeth continue to grow throughout an animals glycoproteins
life (e.g. mouse, rabbit). The opposite condition, with a low-
crowned tooth, is termed brachyodont. These teeth have closed Silk
roots and grow to a fixed length and stop erupting (e.g. human fibroin
teeth). gel
b-chitin
3.3 Carbonates
(d)
From a biological point of view, calcareous shells and tests
are not tissues: they do not contain cells, and are not directly
produced by cells. For example, neither the calcitic prismatic Figure 16 Successive models of the nacreous layer of mol-
unit of the Pinna shell nor the aragonitic nacreous tablet is the lusk shells
BIOMINERALIZATION 11
that soluble and insoluble organic matrices are present. 4.1 Biology
From the composition of these matrices, and from the
ultrastructures, Weiner and Traub have proposed a model The strict control of the organism on its skeletal units and
(Figure 16(c)).34 More recently, this model was improved, their arrangement allows us to use the microstructure and
based on the study of a bivalve shell (Figure 16(d)).35 composition as taxonomical and phylogenetical criteria. The
Thanks to a fixative-decalcification process, the holes in example of the nacreous layer of the mollusk shells has been
the interlamellar membranes were not observed. However, described, and reflects the phylogenetic data: similarities of
the relationships between crystal morphology and surface structures (columnar pattern and radial sectors) between the
interactions with the reactive groups of the organic molecules two sister groups, cephalopods and gastropods, differences
are unclear. with the bivalves (noncolumnar pattern, four twinned sectors).
Besides organic growth modifiers, Mg and Sr play a primary Another example is found in scleractinia corals. There is
role: the incorporation of Mg2+ has been shown to modify a strong relationship between the spatial arrangement of
the morphology, solubility, and polymorphic expression of the septal centers of calcification and the 28 S rRNA
CaCO3 biominerals. Furthermore, Mg is the principal inhibitor phylogeny.39
of calcite growth in natural waters. However, the fundamental Minor element contents and isotopic ratios are used for
mechanistic interactions of Mg with the calcite surface remain physiological purposes. Sr/Ca ratios in bone and teeth are
controversial. In vitro experiments show that Mg contents said to reflect the diet of the animal (herbivores versus
of ACC depend on the Mg/Ca ratio solution, and that Mg carnivores). Stable isotope analysis of teeth and bones
stabilizes ACC.36 provides direct information on the lifetime diets: the nitrogen
isotopes reflect the trophic level of the protein that has been
consumed. Within an ecosystem, they can identify herbivores
3.4 Magnetite and Ferritin
and carnivores, while the carbon isotopes tell mainly about
Among other biominerals, magnetite crystals have a pec- the amount of protein in the diets from terrestrial versus
uliar status. Magnetite biomineralization is a genetically marine ecosystems.
controlled biochemical process having evolved about 2 billion Another unexpected role of some skeletal pieces has been
years ago in the magnetotactic bacteria. Magnetite crystals described.40 Ophiuroids are a large group of Echinoderms
(between 20 and 100 nm) have been extracted from bacteria that includes the brittlestars. They have five arms, superfi-
and some mollusks (chitons).1 They are arranged in a chain cially resembling true starfishes (Asteroidea), and can catch
with gaps between the crystals. All the magnetite crystals that fast motile prey. Aizenberg and coworkers have found that
have been examined to date are single magnetic domains, and calcite crystals in their skeletons act as optical receptors or
it has been suggested that hydrated iron oxide in ferritin (the lenses. However, it is not known whether the system of lenses
major iron storage protein in living organisms) would be the and nerves is actually an eye. However, these structures
precursor of biological magnetite.37,38 are absent in closely related but not light sensitive species of
brittlestars.
Growth lines are a general feature of fossil and modern
mineralized tissues: they are present in the enamel of a
4 APPLICATIONS dinosaur tooth (Figure 17(a)), the calcitic dinosaur eggshell
(Figure 17(b)), or the aragonitic fish otolith (Figure 17(c)).
Otolith growth rings record daily age and growth patterns.41
Studies of biominerals and biomineralization have various But the growth of all the calcified skeletons is not so easy to
applications, from biology to biomimetics. decipher (Figure 17(d)).
Figure 17 Growth lines: (a) Enamel of a dinosaur tooth. (b) Vertical section in a Dinosaur eggshell. (c) Polished and etched section of a fish
otolith. (d) Complex structure of a fossil cephalopod shell (Belopterina)
12 BIOMINERALIZATION
Table 1 Physical properties of elemental Bi These include Na3 In2 Bi3 , Na3 InBi2 , K7 In4 Bi6 , K11 In6 Bi9 ,
and Rb7 In4 Bi6 .8
Atomic weight 208.98 amu
Melting point 271 C
Boiling point 1560 C
2.1.3 Posttransition Metal Compounds of Bismuth
H fusion 10.48 kJ mol1
H vaporization 179.1 kJ mol1
Bismuth is not miscible with cadmium. It is miscible with
Density 9.747 g cm3
S (298.15 K) 56.74 J K1 mol1 mercury but does not form any discrete compound. A simple
Cp 25.22 J K1 mol1 eutectic system is observed with bismuth and zinc. A number
Electrical resistivity 106.8 108 m (273 K) of low-melting alloys are known such as Woods metal (50%
Thermal conductivity 7.87 W m1 K1 Bi, 25% Pb, 12.5% Cd, 12.5% Sn; mp 70 C).1,2 These alloys
Mass magnetic susceptibility 1.684 108 kg1 m3 (s) are often used as heating bath materials, in automatic sprinkler
Coefficient of linear thermal expansion 13.4 106 K1 systems, fire detection devices, safety plugs in compressed
Electronegativity 2.02 (Pauling)
gas cylinders, and so on. Alloys which contain more than
1.67 (Allred)
Radii: ionic Bi5+ 0.74 A 55% Bi expand on freezing and are used in the production
Bi3+ 0.96 A of castings, type metal, and accurate dies. Bismuth and
atomic 1.55 A antimony are completely miscible and alloys with a small
covalent 1.52 A percentage of antimony show large galvanothermomagnetic
van der Waals 2.40 A effects. Bismuth forms compounds of formula MBi with
Ionization potentials:
1st 703 kJ mol1
M = In or Tl. In addition, In also forms the compounds In5 Bi3
2nd 1609 kJ mol1 and In2 Bi, which are superconducting at low temperature.9
3rd 2466 kJ mol1 Bismuth phosphide has been prepared by reaction of BiCl3
4th 4370 kJ mol1 and P(SiMe3 )3 .10
5th 5403 kJ mol1
Ar3 BiX2 (Ar = aryl; X = F, Cl, Br) are well known. BiF5 is occurs. Examples include [BiCl2 (15-crown-5)(MeCN)]SbCl6 ,
a very powerful oxidizing and fluorinating agent. [BiCl(18-crown-6)(MeCN)2 ][SbCl6 ]2 ,24 BiCl3 (12-crown-4),
The bismuth(III) halides are moisture sensitive and are and [BiCl2 (18-crown-6)]2 [Bi2 Cl8 ].25 Hexamethylphospho-
readily converted into the oxyhalides BiOX (equation 1). ramide (hmpa, OP(NMe2 )3 ) also binds to bismuth halides
Addition of acid to aqueous suspensions of the oxyhalides yielding complex halo-hmpa bismuth cations: [Bi2 I6 (hmpa)2 ],
will regenerate BiX3 , which exist as complex halo anions in [BiI2 (hmpa)4 ][I3 ], and [BiI2 (hmpa)4 ][I5 ].26
solution. Addition of ammonium hydroxide to such solutions Halide ions form adducts with BiV or BiIII halides, leading
results in the formation of insoluble Bi(OH)3 , which is easily to complex ions. [BiF6 ] is formed upon reaction of NiF2 with
dehydrated to the oxide. BiF5 in anhydrous HF.27 The resultant Ni[BiF6 ]2 compound
dissolves readily in MeCN giving [Ni(NCMe)6 ][BiF6 ]2 . The
BiX3 + H2 O BiOX + 2HX (1) alkali metal/BiF6 complexes have been prepared by the
reaction of elemental fluorine with various salts.28 For
BiCl3 is very easily hydrated and commercial samples example, LiBiO2 , NaBiO2 , and NaBiS2 are converted into
may need to be dried or sublimed if anhydrous material for the corresponding MBiF6 at 450 500 C. The K+ compound
use in sensitive reactions (e.g. with Grignard reactions) is was prepared from either KBiS2 or a mixture of KCl and
required. Refluxing a thionyl chloride suspension of BiCl3 Bi2 O3 at 360 450 C, while the Rb+ and Cs+ salts arose from
is an effective method for dehydrating the solid. Anhydrous fluorination of mixtures of the alkali metal carbonates and
BiCl3 is soluble in aromatic hydrocarbons and donor solvents Bi2 O3 at 400 450 C. XeF4 reacts with BiF5 in anhydrous
such as ethers where complexes are formed. Bismuth(III) liquid HF to give [XeF3 + ][BiF6 ], in which there is a tight
halides are useful starting compounds for the production of association between one of the F atoms on the bismuth and
many other bismuth(III) compounds.1,2 (see also Bismuth: the Xe. The BiF bond distance is substantially lengthened by
Organometallic Chemistry). this interaction (2.1 A as against ca. 1.9 A).29
A feature commonly found among bismuth(III) complexes
is their ability to function as Lewis acids and expand the 2 3
octet of the bismuth atom (see Hypervalent Compounds). X X
This leads to a number of adducts between the bismuth X X
X X
halides and common donor molecules such as ethers, Bi Bi
amines, phosphines, and organosulfur compounds.15,16 Simple
X X X X
bismuth arene complexes (see Arene Complexes) in which
the aromatic ring is -bonded to the bismuth atom have been X
structurally characterized.17 A similar bonding mode has been (1) (2)
found when AlCl3 is added to BiCl3 in arene solvents.18
Bismuth arene complexation is also observed for the bismuth 3
alkoxides such as [Bi(OC6 F5 )3 (toluene)]2 and Bi4 (4 -O)(- X X
X X
OC6 F5 )6 {3 -OBi(-OC6 F5 )3 }2(C6 H5 CH3 ).1921 The ability X
Bi Bi
to form complexes with arenes is probably dependent on the X
electronegativity of the groups attached to bismuth. X X
X
Ether bismuth halide adducts also exist. Structural work
(3)
on bismuth chloride diethyl ether or THF complexes show
that, at low temperature, polymeric chains of BiX3 linked
by halide bridges exist and that the bismuth atoms may be For BiIII halides and pseudohalides, a wide range of
coordinated by one or two ether molecules.22,23 Bismuth(III) complex anion structures has been observed, including
bromide coordinates three THF molecules.23 These solvent [BiX5 ]2 (1), [BiX6 ]3 (2), [Bi2 X9 ]3 (3), [Bi2 X8 ]2 (4),
molecules are readily removed under vacuum. The polyethers [Bi3 I12 ]3 , [Bi4 X16 ]4 (5), [Bi2 Cl10 ]4 , [Bi4 Cl20 ]8 and
diglyme and diethylcarbitol give dimeric adducts with BiCl3 .21 [Bi8 X28 ]4 .3032 In addition to discrete ions such as (1) (5),
In the presence of cyclic polyethers, simple coordina- polymeric species may result. Thus [BiX4 ]n n adopt edge-
tion, or formation of polyether-coordinated bismuth cations sharing (6) and [BiX5 ]n 2n vertex-sharing (7) octahedral
4 BISMUTH: INORGANIC CHEMISTRY
X X
Bi
X X 2.4 Bismuth Compounds with Oxygen-based Ligands
X X X
Bi Bi 2.4.1 Alkoxides
X X X
X X Because of the interest in a variety of heterometallic
Bi oxides with potentially valuable applications such as high
X X TC superconductivity, oxide ion conductivity, piezoelectric
X properties, and ferroelectric properties, bismuth alkoxides
(5) have been prepared for use as sol gel and vapor deposition
precursor compounds.38 Mehrotra and coworkers found that
Bi(OR)3 (R = Me, Et, Pr) were insoluble and probably
BiX6 configurations. The polymeric anion {Bi2 I7 }n is also polymeric.39 No structural information is available for
known.31 HCl reacts with BiCl3 in ether solution to produce these simple compounds. The t-butoxide complex is
the acid H[BiCl4 ](solvent)x , in which a complex anion (5) soluble, as is the compound for which R = 2,6-Me2 C6 H3 .40
exists. As seen in the structures, the bismuth atoms which These are monomeric as determined by electron or X-
are hypervalent may or may not show stereochemically active ray diffraction. For the case where R = CH(CF3 )2 , the
lone pairs of electrons. compound is a centrosymmetric dimer which also has
coordinated THF.21 These compounds were prepared by
n
the reaction of BiCl3 and an appropriate alkali metal
X alkoxide. The mixed halide methoxide BiCl(OMe)2 has
also been prepared by this method or by pyrolysis of
X X
Bi BiCl(O2 COMe)2 .41 Bi(OSiPh3 )3 is prepared by this salt
X X metathesis method and has low solubility, except as the
X X THF adduct Bi(OSiPh3 )3 (THF)3 (8), which is monomeric and
X
Bi very soluble.42 {BiOSi(Ot Bu)2 Ph}3 has also been prepared.43
X
The related complex Bi(OCPh3 )3 does not show the solvent
X X coordination but the electron demand at the bismuth center
Bi
X X is satisfied by -interactions between the bismuth and one
phenyl ring of each alkoxide ligand.44 Dimeric monoalkoxide
X complexes of the type [Bi(NO3 )2 (triethylene glycolate)]2 have
been synthesized by Rogers and coworkers.45 Higher order
(6) oligomerization is hindered by the chelation by the triethylene
glycolate ligand. Bi(OH)3 reacts with triethanolamine to give
Bi(OCH2 CH2 )3 N.46 The compound is composed of chains
2n
X X of alkoxo-bridged bismuth units.47 The chains are aligned in
X X X pairs with weak BiO interactions between them. Structural
Bi X X
Bi features are similar to those found in many of the bismuth
X X X X
Bi complexes with naturally occurring multidentate carboxylate
X X X
X and alkoxide ligands.
X Another synthetic method to produce alkoxide complexes
(7)
of bismuth employs the solvolysis of {BiN(SiMe3 )2 }3 48 by
alcohols. Bi(OCH2 CH2 OMe)3 has been prepared in this
fashion and is dimeric in the solid state.42,48 The similar
Related complexes with halide ligands and other donors complex with OCMe2 CH2 OMe is also known.49 These
such as THF, pyridine, picoline, or phosphines have been complexes are volatile and may be used for chemical
BISMUTH: INORGANIC CHEMISTRY 5
(8)
2.4.2 Carboxylate Complexes
vapor deposition methods. Solvolysis of organobismuth Bismuth readily forms complexes with organic carboxy-
compounds may also be accomplished using acidic alcohols. lates. These compounds are easily prepared from bismuth(III)
BiPh3 has also been shown to react with C6 F5 OH to give halides and the alkali metal or silver carboxylates or by reac-
[Bi(OC6 F5 )3 (toluene)]2 (9).21 The toluene ligands of (9) are tion of bismuth oxides or bismuth oxycarbonate (BiO)2 CO3
labile and are replaced with two THF ligands when dissolved with carboxylic acids or the acid anhydrides. Bismuth acetate
in that solvent. is commercially available and has been used to effect addition
of acetate to organic substrates. For example, cyclohexenes
react with bismuth acetate in the presence of I2 giving
R
the 1,2-diacetatocyclohexanes. If the reaction is conducted
R O
R in the absence of water, trans-1,2-diacetates are obtained,
O O but if water is present, cis compounds result.57 Carboxy-
Bi Bi
O late linkages from naturally occuring organic acids form
O the basis for many biologically active bismuth compounds
R O R
(discussed in the next section). In addition to Bi(OAc)3 ,
R bismuth formate58 and bismuth trifluoroacetate59 have been
(9) studied. Bismuth trifluoroacetate crystallizes with coordi-
nated trifluoroacetic acid when prepared from reaction of
Bi2 O3 with a mixture of trifluoroacetic acid and trifluo-
Organobismuth alkoxides have been prepared: Et2 BiOEt racetic anhydride.60 The adduct NaBi(O2 CCF3 )4 is formed
and MeBi(OEt)2 are formed from the reaction of Et2 BiBr50 or when NaBiO3 is treated with trifluoroacetic acid.59 Pyrolysis
MeBiBr2 51 with NaOEt. Siloxy derivatives are also known.52 of the formate leads first to BiO(O2 CH) and ultimately to
BiEt3 undergoes partial solvolysis by phenol or C6 F5 OH, (BiO)2 CO3 .
producing [BiEt2 (OAr)] which is a chain polymer with the The bismuth(II) compound [Bi2 (O2 CCF3 )4 ]C6 Me6 com-
alkoxide function bridging between bismuth atoms.53 pound has been prepared in low yield by the pyrolysis
Bismuth alkoxide complexes are easily hydrolyzed and of bismuth(III) trifluoroacetate in hexamethylbenzene. It
complex bismuth oxo-alkoxide compounds may result as possesses a BiBi bond that is bridged by four bridging
intermediates to full hydrolysis. A number of exam- carboxylate ligands in a fashion similar to the tetracarboxy-
ples of these are known for the pentafluorophenox- late complexes of the metal metal bonded transition metal
ide system and include Bi4 (4 -O)(-OC6 F5 )6 {3 -OBi(- dimers.61 Salicylic acid, o-HOC6 H4 CO2 H, has proven use-
OC6 F5 )3 }2 2(C6 H5 CH3 ), Bi8 (4 -O)2 (3 -O)2 (-OC6 F5 )16 , ful for linking bismuth to other metals such as Ti, Ta, or
Bi6 (3 -O)4 (3 -OC6 F5 ){3 -OBi(OC6 F5 )4 }3 , NaBi4 (3 -O)2 Nb owing to the presence of both the phenol and carboxylic
(OC6 F5 )9 (THF)2 , Na2 Bi4 (3 -O)2 (OC6 F5 )10 (THF)2 , [NaBi(O acid functions.62 The salicylate ligand can be found in either
C6 F5 )4 (THF)] , and Na4 Bi2 (6 -O)(OC6 F5 )8 (THF)4 .20,54 A the monodeprotonated form o-HOC6 H4 CO2 and in the di-
hexanuclear compound Bi6 (3 -O)3 (-OR)7 (OR)5 has also deprotonated version o-OC6 H4 CO2 2 giving flexibility in
been observed where R = C6 H3 Cl2 -2,6.55 The formation of both charge and coordination mode. These complexes serve
oxide ligands can arise not only from hydrolysis but also as useful precursors to heterometallic oxides.
from condensation of two phenoxide ligands to produce
bis(pentafluorophenyl)ether. For example, careful addition
of one equivalent of NaOC6 F5 to [Bi(OC6 F5 )3 (toluene)]2 2.4.3 Biologically Active Bismuth(III) Complexes
yields first the adduct [NaBi(OC6 F5 )4 (THF)] as an infi-
nite chain polymer in which there are alternating Bi3+ Bismuth compounds have long been known for their
and Na+ ions with two phenoxides bridging between biological function,6365 primarily for treating gastrointestinal
each metal, but if more phenoxide is added, the ether disorders.64,66 Generally bismuth compounds are not very
6 BISMUTH: INORGANIC CHEMISTRY
toxic owing to low solubility of bismuth salts in solution and in the manufacture of glass and ceramic products, in
have potential for a variety of medicinal applications.63,67 disinfectants, magnets, catalysts, and rubber vulcanization.
Bismuth chloride reacts rapidly with water to form the It readily dissolves in acidic solution yielding complex halide
insoluble subhalide BiOCl and other salts behave similarly. species. High purity material may be prepared by igniting
However, bismuth oxalate is reported to be poisonous. bismuth nitrate. Four crystalline modifications , , , and
Bismuth aluminate, bismuth phosphate, bismuth subgallate, are known, which are monoclinic (pseudoorthorhombic),
and bismuth subnitrate have antacid properties. Several tetragonal, body-centered cubic, and cubic, respectively.
compounds have been used as antisyphilitics, including The thermodynamically stable phase converts to the
bismuth butylthiolaurate, bismuth oxychloride, bismuth phase at 729 C. Upon cooling to 650 C the phase is
tris(ethyl camphorate), bismuth potassium tartrate, bismuth produced and at 629 C the phase is obtained. Bismuth
sodium iodide (Na2 BiI5 ), and bismuth sodium tartrate. oxide has been reported to be an oxygen ion conductor
Bismuth oxide, bismuth subgallate, and bismuth tannate have at high temperatures and this conductivity varies with the
found uses as astringents, and bismuth subnitrate has been phase in the order < < .76 The phase is highly
used in cosmetics. Gastritis and duodenal ulcers may be disordered and reportedly has about 75% of the disorder of
treated with bismuth subcitrate, while bismuth iodide oxide, the molten compound. The oxide is very easily contaminated,
bismuth iodosubgallate, and bismuth tribromophenate find forming compounds which have the same crystal system
uses as anti-infective agents. Bismuth sodium triglycollamate and similar lattice parameters to the body-centered cubic
and bismuth subsalicylate function as suppressants of lupus form. These compounds are based upon a formulation
erythematosus. of [Bi24 O40 ]8 in which contaminant cations complete the
Complexes of bismuth(III) with naturally occurring organic charge balance. Simple compounds with the formula EBi12 O20
acids have been synthesized and studied for potential (E = Si, Ge) are examples. Silicon can be incorporated by
biological activity.6871 Citric acid complexes have long
leaching of that element from porcelain crucibles during
been known to have biological activity and a number have
high-temperature reactions.
been recently synthesized and characterized in solid state
The pentavalent oxide Bi2 O5 is reportedly prepared by
and solution.71,72 Synthetic methods to these compounds are
oxidation of Bi2 O3 in solution or by fusion of Bi2 O3 with
straightforward, as exemplified by the reaction of bismuth
KClO3 .77 The compound is very unstable and has not been
nitrate with L-()-malic acid and L-(+)-tartaric acid to give
isolated in pure form.
bismuth(III) malate monohydrate and tartrate trihydrate,69
Bismuth oxide forms a number of complex mixed-metal
or reaction of Bi(OH)3 with (S)-lactic acid to produce
phases with the divalent metal oxides of calcium, strontium,
bismuth(III) lactate.70 Bismuth salicylate is conveniently
prepared by the reaction of BiPh3 with salicylic acid in barium, lead, and cadmium, and these show a wide variety
refluxing toluene. From this preparation, the structures the in composition. With transition metal oxides, mixed-metal
bipyridine and phenanthroline adducts of bismuth salicylate oxide phases have been observed which are based upon a
have been reported.73 While the bipyridine simply adds to Perovskite-type lattice (10) containing layers of Bi2 O2 .78 It
Bi(HOC6 H4 CO2 )3 , the addition of phenanthroline results is notable that the high Tc superconducting materials which
in the elimination of salicylic acid and the deprotonation include bismuth40 also have this Perovskite-type of lattice with
of one of the other salicylate ligands. In both cases, layers of copper oxide interleaved with bismuth oxide layers.
the high Lewis acidity of the bismuth center gives rise
to dimer formation: [Bi(HOC6 H4 CO2 )3 (bipyridine)]2 and
[Bi(HOC6 H4 CO2 )(HOC6 H4 CO2 )(phenanthroline)]2 .
While the mechanism of the interaction of these carboxylate
complexes with the biological molecules that leads to
their activity is not well understood, there is some
evidence that the molecules can bind to N-donor and S-
donor molecules in proteins. Bismuth(III) has been shown
to bind most strongly to the thiolates in glutathione.74
There is some evidence that Bi(III) can replace metals
such as Fe(III) in lactoferrin and transferrin or Zn(II) in
metallothionein.75
The alkali metal oxides MBiO2 (M = Na, K, Rb, Cs) have proposed mechanism for the SOHIO process for the oxidation
been prepared and structurally characterized.79 The bismuth and ammoxidation of propene using a molybdenum bis-
has a +5 oxidation state in sodium bismuthate (NaBiO3 ), muthate catalyst.81 The intermediates proposed in Scheme 1
a well-known but ill-defined substance which has been have not been observed in discrete molecular systems. Indeed,
used as an analytical reagent capable of oxidizing Mn2+ no molecular molybdenum bismuth oxide species is known.
to Mn7+ . The solid has the ilmenite structure (FeTiO3 ). The reaction of BiPh3 Cl2 with [Bu4 N]2 [MoO4 ] has been
It dissolves in strong acid solutions to give an as yet examined82 and the products identified as (BiPh3 MoO4 )x and
uncharacterized bismuth(V) complex which is stable for a few [BiPh3 (MoO4 )2 ]2 , but these compounds may be more appro-
days in solution. Other phases containing BiV have recently priately considered organobismuth derivatives than bismuth
been reported.80 These include LiSr3 BiO6 , NaSr3 BiO6 , oxide models.
NaBa3 BiO6 , Li6 KBiO6 , Li6 RbBiO6 , and Li2 Ba5 Bi2 O11 Saturated hydrocarbons may also be oxidized by bismuth
produced in molten salt reactions. oxide catalysts. For example, methane is converted to CO2 and
The importance of bismuth oxide species in oxidation of a mixture of higher hydrocarbons over bismuth oxide catalysts
organic molecules is illustrated in Scheme 1, which shows a that also contain sodium, calcium, cesium, and/or halide
H O
O
O O Mo H
O
O Mo O
O Mo O Bi O
O Bi O
Bi O O
O
O
NH3 +NH3 H
acrolein N H
H
H
N O Mo
H N
H
O Mo N Bi O
H N H O
Bi O
O
O Mo N H
Bi O
O
H
H
N H
+ 1/2 O2 +1/2 O2 NH3 H
H2O O
O Mo N
Mo H
Bi O
Bi O O O
N C
O
acrylonitrile
Scheme 1
8 BISMUTH: INORGANIC CHEMISTRY
ions.83 Propane has been oxidized to acrolein over a silver- compounds include NaBi3 (3 -O)(OR)8 (THF), NaBi4 (3 -
doped bismuth vanadomolybdate catalyst.84 Heterometallic O)2 (OR)9 (THF)2 , Na2 Bi4 (3 -O)2 (OR)10 , and Bi6 (3 -
bismuth oxides containing vanadium, titanium, niobium, or OR)(3 -O)4 [3 -OBi(OR)4 ]3 , which have been obtained
tantalum have also been shown to serve as photocatalysts for from the reaction of BiCl3 and NaOC6 F5 . The reaction
a variety of reactions including the splitting of water.85 of [Bi(OC6 F5 )3 (toluene)]2 with NaOC6 F5 led to the
production of Bi6 (3 -O)2 (4 -O)(OR)12 and NaBi3 (3 -
O)(OR)8 (THF)3 . Reaction of BiPh3 with HOC6 F5 in
2.4.5 Bismuth Oxo Cluster Complexes and Related THF led to the formation of Bi6 (3 -OR)(3 -O)4 [3 -
Compounds OBi(OR)4 ]3 (THF)2 . Bi6 (3 -OR)(3 -O)4 [3 -OBi(OR)4 ]3 and
Bi6 (3 -OR)(3 -O)4 [3 -OBi(OR)4 ]3 (THF)2 possess the core
In very acidic solutions, bismuth(III) exists in the form of geometry in (12).54
the nonaaquo ion [Bi(H2 O)9 ]3+ , which is similar to the aquo
complexes of the lanthanide ions,86 but partial hydrolysis of
bismuth(III) salts leads to the formation of bismuth oxo 2.5 Bismuth Chalcogenide-based Ligands
clusters. The core structure of these complexes is often
based upon a Bi6 octahedral core with oxide, hydroxide, 2.5.1 Compounds with Organochalcogenide Ligands
or alkoxide functions bridging the edges and/or faces of the
octahedron. The [Bi6 (OH)12 ]6+ ion (11) has been studied Bismuth very readily forms complexes with sulfide and
spectroscopically.87 In oxo clusters, the octahedron is face- sulfur-containing ligands, and this ability may be important in
bridged by eight oxo or alkoxide functions (12). Such core understanding the biological activity of colloidal bismuth
structures have been found in the hydrolysis of bismuth nitrate carboxylate complexes. The crown thioether compounds
or perchlorate.88 [9]aneS3 , [12]aneS4 , [15]aneS5 , [18]aneS6 and [24]aneS8
add to BiCl3 .90 The bismuth is bonded to each sulfur
and the BiCl bonds are retained, as has been established
6+
for the [12]aneS4 and [15]aneS5 complexes, (13) and
Bi (14). The BiCl distances are on the order of 2.57 A
OH
and the BiS distances range from 2.98 to 3.25 A.
HO
OH The compound [SMe3 ]2 [Bi2 I8 (SMe2 )2 ] has dimethylsulfide
HO
bonded to bismuth,91 and the tridentate MeSi(CH2 SMe)3
Bi
HO Bi OH reacts with BiX3 (X = Cl, Br) to displace the halide ions
Bi forming [Bi(MeSCH2 )3 SiMe)]X3 which is polymeric in the
HO Bi OH solid state.92
HO OH
OH
HO Bi
S S S
S S
S S S S
(11)
Bi
Bi
2+ Cl Cl Cl Cl
Bi
Cl Cl
O O O O (13) (14)
Bi Bi
Bi BiEt3 reacts with thiols and the likely product is Bi(SR)3 ,
Bi O which has not yet been fully characterized;93 however, such
O O complexes have been synthesized via other methods.94 The
O
organic thiolates RS examined include those with R = C6 F5 ,
Bi 4-MeC6 H4 , 2,6-Me2 C6 H3 or 3,5-Me2 C6 H3 . The structure of
BiSC6 H2 -2,4,6-{(CMe3 )3 }3 from the reaction of BiCl3 with the
(12) lithium salt of the thiolate has been reported.95 Bismuth nitrate
reacts with 3 equivalents of (3-trimethylsilyl)pyridine-2-
thiol to yield the tris{(3-trimethylsilyl)pyridine-2-thiolato}Bi
A number of bismuth alkoxo-oxo cluster complexes complex96 which, by comparison with the antimony analog,
have been observed in the C6 F5 OH system.1921,54,89 These should have the three ligands chelating the bismuth atom
BISMUTH: INORGANIC CHEMISTRY 9
Bi Co(CO)3
(OC)3Co
Bi
(OC)3Co Bi
Bi
Co(CO)3
(26)
MLn1 = Co(CO)3
MLn =
Co(CO)4 MLn = Bi
Mn(CO)5 Co(CO)4
CpFe(CO)2 Bi CpFe(CO)2
LnM MLn 3 CO Ln1M MLn1
CpMo(CO)3
BiCl3 + 3 [MLn] MLn
MLn1
(24) (25)
(OC)3Co Bi Co(CO)3
Co(CO)4 Bi
Bi (OC)2Co Co(CO)2
(OC)4Co Co(CO)4 C
Co(CO)4 O
(28) (27)
Na napthalenide
[Bi2Co4(CO)11]2
Scheme 2
(see Hypervalent Compounds).153 The BiCo distances in the same structure as (27) based upon the structures of
this molecule are very long (ca. 2.9 A) and the lone pair [Sb2 Co4 (CO)11 ]n (n = 1 or 2) which have both been
is stereochemically inactive. The ability of the bismuth reported.157 For that redox pair the major change upon
atom to act as an acceptor may be key in reactions of reduction is lengthening of the CO-bridged CoCo bond
clusters with nucleophiles. The bismuth centers in these by about 0.135 A. The bismuth compounds are more sensitive
molecules can also act as Lewis acids toward halide ions to oxidation and fragmentation than are the antimony analogs.
or other donor ligands as exemplified by the formation of NaBiO3 may also be used to introduce Bi atoms into
[Cl2 Bi{Fe(CO)2 Cp}2 ] , {[OP(NMe2 )3 }2 Bi{Fe(CO)2 Cp}2 ]+ , metal clusters, as has been demonstrated in the case of iron
[Fe(CO)4 Bi2 Cl4 (-Cl)2 ]2 , [Bi3 Cl4 (-Cl)4 {Fe(CO)3 }]3 , and (Scheme 3), osmium, ruthenium, chromium, and molybdenum
[(-H)Fe2 (CO)6 Bi2 {(-Cl)2 } ]n .154,155 carbonyls. This reaction works best for Fe(CO)5 in methanolic
The cubane cluster Bi4 Co4 (CO)12 (26) is a thermodynamic KOH, where [Bi{Fe(CO)4 }4 ]3 (29) is produced cleanly and
sink in a number of reactions of the other BiCo carbonyl in high yield.158 Similarly, reaction of Cr(CO)6 with NaBiO3
compounds.149 It does not appear to be stable to substitution at room temperature in methanol leads to [Bi{Cr(CO)5 }4 ]3 or
or to reduction, but detailed chemistry of this compound has to [MeBi{Cr(CO)5 }3 ]2 at 80 C.159 If the NaBiO3 /Fe(CO)5
not been reported. reaction is carried out with heating in the absence of KOH,
Electrochemical reduction of BiCo3 (CO)9 (25) or pyrol- the cluster product is [BiFe3 (CO)10 ] (35).160 Alkylation of
ysis of (28) produces the unusual cluster compound (35) occurs at the 3 -CO rather than at Bi, giving (36),
[Bi2 Co4 (CO)11 ] (27) (Scheme 2).156 This compound is illustrating the low basicity of the main group atom.161
reduced to a dianion that is believed to have essentially Compound (31) is the starting point for a wide number
BISMUTH: INORGANIC CHEMISTRY 13
Fe(CO)4 3
Fe(CO)4
1. KOH/MeOH 2 [Cu(MeCN)4]BF4 (OC)4Fe
Fe(CO)5 Bi Bi
2. NaBiO3 (OC)4Fe Fe(CO)4 (CO)4Fe
Fe(CO)4 Fe(CO)4
(29) (31)
BiX3 NaBiO3
NaBiO3
MeOH 2 MeOH
X H+ 2
or BiCl3 Fe(CO)4
Bi
LnFe FeLn
Bi
FeLn 2 [Cu(MeCN)4]BF4
(30) Bi Bi (CO)3Fe Fe(CO)3 Fe(CO)3
[Fe(CO)4]2
Bi
Fe(CO)3 + (CO)3Fe
H Fe(CO)3
(CO)3Fe Bi
Fe(CO)3
(CO)3Fe Fe(CO)3 H Fe(CO)3 H
(32)
Fe(CO)3 Bi
(34) (33)
C
O CO [Co(CO)4]
CH2Cl2
(35)
Bi
CH3SO3CF3
Fe(CO)4 2 (CO)3Fe
Co(CO)4
(CO)4Fe
Bi Bi Bi
(CO)3Fe Fe(CO)3
Fe(CO)3 Fe(CO)3 (38)
Fe(CO)3 (CO)3Fe
C Bi Bi
Me O Bi
(36) (37)
Scheme 3
of BiFe carbonyl complexes. Addition of BiCl3 to (31) compound based upon a tetrahedral array of Bi atoms with
results in the formation of [XBi{Fe(CO)4 }3 ]2 (30), which Fe(CO)3 groups capping three of the triangular faces (it is
appears to be a simple substitution of X for [Fe(CO)4 ]2 , but discussed further below). Compound (29) will react further
this exchange does not occur with [Et4 N]X and probably with NaBiO3 to form [Bi2 Fe4 (CO)13 ]2 (32),166 which is
is initiated by initial oxidation of (31). The structurally based upon a square pyramidal Bi2 Fe3 arrangement of metal
related [RBi{Fe(CO)4 }3 ]2 (R = Bu, PhCH2 ) are obtained atoms. Compound (32) also arises when [Fe(CO)4 ]2 adds to
when [Bi{Fe(CO)4 }4 ]3 is treated with the organic halides, (33). This can be viewed as formally adding two electrons to
although cyclic [RBiFe(CO)4 ]2 compounds may also be the Bi2 Fe3 cluster core, giving rise to FeFe bond cleavage
obtained.162 The latter complexes show Bi2 Fe2 ring structures, as predicted from simply electron counting considerations.
but the R = butyl compound has also been crystallized in Oxidation of (32) regenerates (33). A series of compounds of
a polymeric form.163 Reaction of (32) generated in situ the general form [{Fe3 (CO)9 EMLn }2 ] have been examined and
with Cr(CO)5 (THF) produces the mixed-metal compound the structural parameters associated with the main group atom
[Bi{Fe2 (CO)8 }{Fe(CO)4 }{Cr(CO)5 }] . Compound (31) is can be interpreted in terms of the hybridization at that atom.167
protonated to yield a mixture of Bi2 Fe3 (CO)9 (35) and The compound Fe3 (CO)9 [BiFe(CO)2 {Fe(CO)2 C5 H3 t Bu2 }2 ],
H3 BiFe3 (CO)9 (34). The first can be viewed as arising via another square pyramidal cluster, is obtained when
an oxidation of (31), while the second as a protonation {(CO)2 C5 H3 t Bu2 }(CO)2 FeBiCl2 is treated with [Fe
reaction with subsequent loss of CO and a metal fragment. (CO)4 ]2 ,34 and the isoelectronic asymmetric species
Compound (29) is also oxidized by [Cu(NCMe)4 ]BF4 to Fe3 (CO)9 {SeBiFe(CO)2 C5 H4 t Bu} is formed when [Fe3 (CO)9
give a monoanion with an FeFe bond (31). This compound Se2 ]2 is treated with (C5 H4 t Bu)Fe(CO)2 BiCl2 .168 Addition
is unstable and decomposes to [Bi4 Fe4 (CO)13 ]2 (37) upon of [Co(CO)4 ] to (33) leads instead to vertex replacement
standing in solution.164,165 This product is a very interesting and the formation of [Fe2 (CO)6 Bi2 (-Co(CO))4 ] (38).169
14 BISMUTH: INORGANIC CHEMISTRY
Ru(CO)4
R
(OC)4Ru
Bi H Ru(CO)4 (42)
(CO)4Ru
Ru(CO)4
Of particular interest is the observation of different isomers
(39) for Bi2 Ru4 (CO)12 (40) and Bi2 Os4 (CO)12 (41).
Antimony iron carbonyl clusters show similarities to
the bismuth iron compounds as well.172 A key difference
Bi between the antimony- and bismuth-containing complexes is
that the bismuth atom is generally less basic and more Lewis
(OC)3Ru Ru(CO)3 acidic than the antimony atoms in corresponding compounds.
(OC)3Ru Ru(CO)3 Reaction of [Ni6 (CO)12 ]2 (1) with RBiCl2 gave icosahedral
[Ni10 (CO)18 (BiR)2 ]2 (R = Me, Et; (42)) as the major prod-
uct. These molecules possess noncentered 1,12-Ni10 Bi2 icosa-
Bi hedral cages as do the other members of the homologous series
(40) [Ni10 (CO)18 (EMe)2 ]2 (E = P, As, Sb).173 Metal-centered
versions of these cluster geometries are also known from the
reaction of BiCl3 with [Ni6 (CO)12 ]2 (equation 2, (43)).174
Os(CO)3
THF
[Ni6(CO)12]2 + 0.5 0.7 BiCl3
(OC)3Os Bi
(OC)3Os Bi n
Bi
Ni
Ni Ni
Ni Ni
Os(CO)3
Ni
(41) Ni Ni
Ni Ni
Ni
Some analogous ruthenium- and osmium-bismuth clus-
ters have been found.171 Examples include Bi2 M3 (CO)9 Bi
and H3 BiM3 (CO)9 (M = Ru, Os). The structures of the (43)
hydride compounds have both been determined and they
Cluster core structure of [Bi2Ni10(m12-Ni)(CO)18]n
are isostructural with the iron complexes as is Bi2 Ru3 (CO)9
with Bi2 Fe3 (CO)9 . The structure of Bi2 Os3 (CO)9 , on the other (2)
hand, has not been determined and its IR spectrum indicates
that it probably has a different structure. A spirocyclic cluster The reaction of [W2 (CO)10 ]2 with BiCl3 gives rise to a
[Ru2 (CO)8 (4 -Bi)Ru3 (CO)10 (-H)] (39) has been reported. neutral compound Bi2 {-W(CO)5 }3 (44), in which the BiBi
BISMUTH: INORGANIC CHEMISTRY 15
Bi Co
Co
W(CO)5 Co
(OC)5W Co Bi
Bi
W(CO)5
Bi
Bi Co
Bi
Co
(44) Co Co
Co
Bi (47)
Sm Sm
Bi
Co
Co
Co
Co Bi
Bi
(45) Bi
Bi Co
2+ Co
L Co Co
L
Co Bi
Sb Bi
Pd Pd
L L
Bi
Sb Bi Co
L
Pd Co
Sb Sb Co Co
Pd
L Co
L Cluster core structure of [Bi8Co14(CO)20]2
L
(48)
(46)
to lead to interesting products. Thus, when the Zintl (c) X. Li and A. A. Gewirth, J. Am. Chem. Soc., 2003, 125,
phase K5 Bi4 is treated with 4,7,13,16,21,24-hexaoxa-1,10- 7086; (d) B. K. Niece and A. A. Gewirth, Langmuir, 1996, 12,
diazabicylco[8.8.8]hexacosane (crypt) and Cr(CO)3 (mesity- 4909; (e) I. Oh, M. E. Biggin, and A. A. Gewirth, Langmuir,
lene) or Mo(CO)3 (cycloheptatriene), the trigonal bipyramidal 2000, 16, 1397.
[Bi3 M2 (CO)6 ]3 (M = Cr, Mo) complexes are formed.133 8. S. Bobev and S. C. Sevov, J. Sol. St. Chem., 2002, 163, 436.
The two transition metal atoms are located in equatorial 9. R. Kubiak, Z. Anorg. Allg. Chem., 1977, 431, 261.
positions, leading to the analysis of the bismuth fragment as
10. (a) C. J. Carmalt, A. H. Cowley, A. L. Hector, N. C. Norman,
a bent Bi3 3 , which is isoelectronic and isostructural with
and I. P. Parkin, J. Chem. Soc., Chem. Commun., 1994, 1987;
ozone. Further exceptions to the cluster-electron counting
(b) G. C. Allen, C. J. Carmalt, A. H. Cowley, A. L. Hector,
rules are [Bi4 Co9 (CO)16 ]2 (47) and [Bi8 Co14 (CO)20 ]2
S. Kamepalli, Y. G. Lawson, N. C. Norman, I. P. Parkin, and
(48), which arise upon oxidation of the reaction product of
L. K. Pickard, Chem. Mater., 1997, 9, 1385.
[Bi2 Co4 (CO)11 ] and Mo(CO)3 (toluene). These compounds
are based upon close-packing of metal atoms and do not have 11. E. Amberger, Chem. Ber., 1961, 94, 1447.
closed-shell electronic configurations.179 12. W. Jerzembeck, H. Burger, L. Constantin, L. Margules,
J. Demaison, J. Breidung, and W. Thiel, Angew. Chem., Int.
Ed. Engl., 2002, 41, 2550.
13. (a) R. W. Zoellner, Chemtracts, 2002, 15, 637; (b) E. J. Baran,
3 RELATED ARTICLES Z. Naturforsch., 2003, 58A, 126; (c) X. Wang, P. F. Souter,
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Bismuth: Organometallic 2 TRIVALENT ORGANOBISMUTH COMPOUNDS
CF3 CF3 have been reported, include Ni(CO)3 BiR3 , M(CO)5 BiR3
(R = Et, t-Bu), [Et4 N][CpV(CO)5 BiEt3 ], CpV(CO)3 BiEt3 ,
and CpV(CO)2 (BiEt3 )2 .38,39 The complex Fe(CO)4 (BiPh3 )2
O was reported a number of years ago40 but attempts to repeat
Bi that preparation have not been successful. Instead, the cluster
complex Bi2 Fe3 (CO)9 is obtained, pointing up a complication
NH2 in the formation of triorganobismuth-metal complexes: the
weakness of the BiC bond. This property results in facile
(4) redistribution reactions or the loss of organic functions from
bismuth with the building of higher nuclearity metal com-
red and a black modification.29 This has been com- plexes. Thus, reactions between BiPh3 and metal halides often
monly found for cyclopentadienyl derivatives of bismuth: give Ph2 BiX and not Ph3 Bi metal complexes. In contrast to
tris(pentamethylcyclopentadienyl)bismuth and CpBiCl2 also these findings, BiPh3 reportedly forms 1:2 adducts with UCl5 ,
exhibit red/black isomerism. The Cp rings are -bound in and 1:1 and 1:2 adducts with NbCl5 .41 These formulations
CpBiCl2 ,30,31 but the -interaction is asymmetric and involves have not, however, been confirmed by X-ray diffraction and
2 - and 3 -coordination to the bismuth atom. CpBiCl2 is in light of the other reports may be questioned.
polymeric, being held together by intermolecular Cl Bi
bridges (5), which further illustrates the ability of the bis-
2.5 Uses of BiR3 Compounds
muth atom to function as a Lewis acid. -Bonding may be
involved in the tris(allyl) complex, but its structure is not yet BiR3 compounds have a number of uses. They are effective
known. cocatalysts for the polymerization of substituted acetylenes by
MoCl5 or WCl6 .42 BiPh3 can act as a radiopacifying additive
for polymeric materials such as polystyrene, poly(vinyl
chloride), polyacrylates, and polyethylenes, with which it
Bi forms homogeneous mixtures. Leaching from the polymer
Cl Bi Cl
Cl Cl can be prevented by using styryldiphenylbismuth, which
Cl Bi
Cl Cl Cl copolymerizes. BiR3 compounds have been used for preparing
thin films of bismuth or bismuth oxide, and for incorporating
bismuth into thin films of high Tc superconductors.
(5) Organobismuth derivatives may undergo solvolysis with
compounds that have acidic protons to replace one or more
Simple arene solvates of bismuth(III) halides and of the organic functions. The production of bismuth alkoxides
pseudohalides have been structurally characterized, as have and biologically relevant bismuth complexes has been accom-
adducts prepared in the presence of AlCl3 .3234 The solid- plished in this way (see Bismuth: Inorganic Chemistry).
state structures of these compounds show -coordination of BiPh3 reacts with HOC6 F5 in toluene to give the dimeric
the arenes to the bismuth centers, as well as intermolecular alkoxide complex [Bi(OC6 F5 )2 (-OC6 F5 )(toluene)]2 (6),34
Bi X bonding that produces dimers or polymeric structures. while BiEt3 reacts with HOPh or HOC6 F5 to give the
Arene complexes that have been structurally characterized polymeric [Et2 BiOAr] (7).43 Two phenyl groups are dis-
include those of benzene, o-, m- and p-xylene, mesitylene, placed when BiPh3 is treated with maleic acid to give
and hexamethylbenzene.32 -Coordination of arenes has PhBi(O2 CCH=CHCO2 H)2 . The maleic acid functions are
also been seen in [Bi(OC6 F5 )3 (toluene)]2 and Bi4 (4 -O)(- themselves displaced when the complex is treated with
OC6 F5 )6 {3 -OBi(-OC6 F5 )3 }2(C6 H5 CH3 ).34,35 Na[dtc].44
Et Bi
Et 2.7 Lewis Acidity of Organobismuth Compounds
O Et
Bi Just as bismuth complexes with inorganic substituents
Et
are Lewis acids, so are their organobismuth analogs (see
O Bismuth: Inorganic Chemistry). Lewis acidity is enhanced
by the presence of the electronegative ligands, which
Bi tend to make the bismuth centers more electropositive.
Et
Et This feature can reduce the solubility of the aryl bismuth
halides through intermolecular halide bridges as observed
(7) for Ph2 BiCl, PhBiBr2 , and MeBiCl2 .51 Not surprisingly
then, RBiX2 (R = Me, Ph) can be isolated as THF,
bipyridine, or phenanthroline adducts in which there are
method has been used for preparing other alkylbismuth
halides. also Bi X intermolecular contacts.46,52 In some cases,
weak interactions are seen between the bismuth atom
and the aryl rings of an adjacent molecule. In addition to
BiCl3 + 2BiPh3 3BiPh2 Cl (3)
solvent adducts, organobismuth halides also form complexes
with added halide ions. Structurally characterized examples
Organobismuth(III) halides may be prepared by elimi- include [Et4 N][Ph2 BiI2 ] (8) and [Et4 N]2 [Ph2 Bi2 Br6 ] (9).33
nation of aryl halide from triarylbismuth(V) dichlorides or In the iodide complex, the bismuth has a distorted square-
dibromides upon heating (equation 4). Presumably, a bis- pyramidal geometry in which one phenyl group is in the axial
muth(V) compound is the intermediate when triarylbismuth position. The square base is defined by the second phenyl
compounds are treated with iodine or when trialkylbis- group, two iodide ligands at 3.0517(8) and 3.1415(8) A, and
muth complexes are treated with chlorine, bromine, or a close contact to an iodide ligand in an adjacent molecule at
iodine, but the intermediates have not been isolated and 4.0850(11) A, giving the compound an asymmetric, dimeric
organobismuth halides are obtained directly (equation 5). The nature. In (9), the phenyl group in the square base has been
tris(trifluoromethyl)bismuth behaves like the trialkyl com-
pounds without the observation of a bismuth(V) intermediate.9
Ph 2
BiAr3 X2 BiAr2 X + ArX (4) Ph I
I
BiAr3 + I2 Ar2 BiI + ArI (5) Bi Bi
I I Ph
Ph
Aryl groups appear to be preferentially cleaved with acids,
so that addition of HX (X = Cl, Br) to Ph2 BiMe leads to (8)
MeBiX2 .46 Ph 2
Cyclopentadienyl halide complexes have been prepared
from the reaction of NaCp or LiC5 Me5 and BiCl3 .47 As Br Br Br
Bi Bi
described earlier, CpBiCl2 , in its red crystal morphol- Br Br Br
ogy, has been structurally characterized (5) and shows a Ph
chain polymeric structure containing both 2 - and 3 -
coordination of the Cp ring to bismuth. In (C5 Me5 )2 BiCl, the (9)
BISMUTH: ORGANOMETALLIC CHEMISTRY 5
Ph
Ph
Bi
OC + NaX
Ph2BiX + Na2[Fe(CO)4] Fe CO
OC
C
O
Ph2BiX
Ph
Ph
Bi
OC CO
Fe Ph
OC Bi
C
O Ph
(10)
O R O
C C
O C
MeI Fe
Bi C O
[Bi{Fe(CO)4}4 ]3 Fe
O C C
Bi C O
BuBr C
O
R O
(12)
Bu 2
Bi
(OC)4Fe Fe(CO)4 Bi
Fe(CO)4
(OC)3Fe Fe(CO)3
Fe(CO)3
(11)
Bi
Scheme 1
Mo, W x = 3; M = Fe, x = 2), giving MeBi[CpM(CO)x ]2 other metals that are toxic. For example, bismuth metal
instead of the expected Me2 Bi[CpM(CO)x ].63 Reac- catalyzes the addition of allyl halides to ketones in the
tion of [Bi{Fe(CO)4 }4 ]3 with alkyl halides leads to absence of a solvent, and presumably proceeds via Bi(III)
[RBi{Fe(CO)4 }3 ]2 (11) or [RBiFe(CO)4 ]2 (12).64 For R = intermediates.66 Bismuth triflate has proven particularly use-
Bu, two forms are observed. One is the usual cyclic Bi2 Fe2 ful and has been widely examined recently.6769 Reactions
core, while the other shows a polymeric chain of BiFe units.65 catalyzed by this salt include Diels Alder reactions, acyla-
ClBi[CpMo(CO)3 ]2 + K[HBEt3 ] EtBi[CpMo(CO)3 ]2 (12) tions, allylations, and Michael additions among many others.
Bismuth chloride has also been used for these same catalytic
Tetraorganodibismuthines and cyclic bismuthines are organic transformations,68,70,71 but it is sensitive to hydroly-
useful for the preparation of metallated diorganobismuth sis, producing the insoluble BiOCl. Bismuth triflate, on the
complexes, as described in Section 2.11. other hand, has been used successfully in the presence of
water.69
Organobismuth(III) complexes may mediate a number of
2.10 Organic Transformations Involving BiIII
reactions involving allylic compounds and aldehydes. In these
Complexes
reactions, an allyl halide is treated with a bismuth(III) salt
Bismuth salts are known for promoting a variety of organic such as BiCl3 and a reducing agent (Zn, Fe, or Al) in the
reactions, and may have considerable advantages in replacing presence of an aldehyde (equation 13).71,72 A likely reaction
BISMUTH: ORGANOMETALLIC CHEMISTRY 7
mechanism involves the reduction of the bismuth halide to an A number of bismuth/metal oxides are used in the
activated metal powder, which can then oxidatively add the catalytic oxidation of hydrocarbons, and in the oxidation and
organic halide. In cases reported to date, these intermediates ammoxidation of alkenes. These transformations are described
have not been isolated or characterized. Some substantiation briefly in Bismuth: Inorganic Chemistry.
for this comes from the fact that aldehydes can be allylated in
the presence of bismuth powder.
2.11 Molecules with BiBi Bonds: Dibismuthines,
H Dibismuthenes, and Cyclobismuth
R1 O BiCl3 O
Reactions of R2 BiX (X = halide or R) with two
+ Zn or Fe R3 equivalents of sodium in liquid ammonia followed by
R2 X R3 H
R2 R1
X = Cl, Br treatment with a dihaloethane results in the formation of the
(13) dibismuthines R2 BiBiR2 (13, R = Ph, Me, Et, Pr, i-Pr, Bu,
Mes; equation 18).7476 The heterocyclic derivative 2,2 ,5,5 -
tetramethylbibismole (14) has been similarly prepared from 1-
Bismuth(III) acetate reacts with cyclohexene to produce
phenyl-2,5-dimethylbismole (see Section 2.12).77 Presumably
1,2-diacetatocyclohexane. If conditions exclude water, a
Na+ R2 Bi is an intermediate, but it has not been
trans configuration arrangement of the two acetate groups
isolated. The related LiBi(SiMe3 )2 DME complex has,
is obtained, while the configuration is cis if water is included
however, been structurally characterized and is converted
in the reaction (equations 14 and 15).73
to the tetrakis(trimethylsilyl)dibismuthine upon reaction
with 1,2-dihaloethane.78 Reduction of Ph2 BiI using Cp2 Co
OAc
AcOH produces Ph2 BiBiPh2 , with the advantage that the Cp2 CoI
3 + 2Bi(OAc) 3 + 3I2 3
can be recycled (equation 19). Some dibismuthines are
OAc thermochromic, as are similar diantimonides.6,79
+
2BiI3 R R
(14) NH3(l)
2BiR2X + 2Na R
Bi Bi + 2NaX (18)
C2H4Cl2
3 + 2Bi(OAc)3 X = alkyl, aryl R
(13)
OAc THF
AcOH 2BiPh2 I + 2Cp2 Co R2 BiBiR2 + 2Cp2 CoI (19)
+ 3I2 + 3H2O 3 + 2BiI3 + 3AcOH
OAc
(15)
R Bi + Cp2ZrCl2
R
R
Bi
Bismabenzene (18) has been prepared according to
(OC)5W Bi Scheme 2.90 The complex is not stable and will add 1,1,1,4,4,4-
W(CO)5 hexafluorobutyne to give (19). In solution at low temperature,
(15) the complex appears to exist as the Diels Alder dimer (20),
R
but raising the temperature gives an NMR spectrum consistent
with (18).
The heterocyclic complexes incorporating other main group
Bi
element atoms have been prepared via the reaction of RBiBr2
(OC)5W Bi with an appropriate difunctional salt or chelating ligand (see
equations 7 and 8). The compound (21) is reported to have
R anticoccidial and insecticidal properties, as do other RBi(SR)2
(16) compounds.
BISMUTH: ORGANOMETALLIC CHEMISTRY 9
CF3 CF3 These reagents also cleave glycols (equations 27 and 28),
CF3 and under the appropriate conditions function as aryl
CF3 O group transfer reagents (equations 29 33). These examples
O are only a small representation of the work that has
Bi R
been done in this area.108 Reactions of cis-cyclohexane-
Ar
Bi O 1,2-diol, meso-butane-2,3-diol, and meso-cyclopentane-1,2-
Ar diol with Ph3 Bi(OAc)2 in the presence of catalytic
Cl CF3 amounts of Cu(OAc)2 have been studied.109 In the case
CF3 of the cyclopentanediol, phenylation occurred giving a
(24) (25) racemic mixture of the phenoxycyclopentanol. Optical
selection was obtained when the reaction was carried
out in the presence of one of the enantiomers of chiral
CF3 CF3 2-pyridyloxazolines. Alkoxide complexes are implicated
CF3 as intermediates in some of these reactions, and for
CF3 one case such a complex, (3,5-(t-Bu)2 C6 H3 OBiPh3 Cl),
O
O has been isolated. The aryl group transfer reaction is
Bi thought to proceed via a nonionic, nonradical concerted
R mechanism.
R
(26) + (p-C6H4OMe)3BiX2 O
OH
Base
(24)
These two molecules are rare examples of bismuth(V) alkyl
-Bi(p-C6H4OMe)3
complexes. X
Reactions of Ar3 BiX2 with organolithium reagents are base-H+
common for producing Ar5 Bi complexes. Unstable, purple
Ph5 Bi was the first of these to be synthesized.100 Interesting Ph3BiCO3
variations in the structure and color of these complexes as OH O O (25)
a function of Ar have been reported.101 The color of BiPh5
has been attributed to relativistic effects.102 A series of BiAr5
OH Ph Ph
complexes have been structurally characterized. The nature
of the aryl ligands is important in determining whether the O O
Ph3BiCO3
structure of those complexes is trigonal bipyramidal or square (26)
planar, which is also related to their color.103 HO OH
In addition to exchange reactions, a halide ion can be Ph Ph
abstracted from the bismuth of Ar3 BiX2 complexes to give OH BiPh3 O
[Ar3 BiX]+ ions. As mentioned before, Ar3 BiI2 has not been N-bromosuccinimide
isolated as it apparently undergoes immediate elimination, (27)
K2CO3
but at low temperatures, in the presence of AgAsF6 the OH MeCN, 1% H2O O
complex, [Ar3 BiI][AsF6 ] has been isolated.104 This complex
R2
has been reported to be a better bactericide than Ph3 Bi. The R1 OH BiPh3 O O
complex [Ph4 Bi][MeC6 H4 SO3 ] is similar, but the tosylate N-bromosuccinimide
anion is weakly bound to the bismuth atom (dBiO = 2.77 A), +
K2CO3
giving it a distorted trigonal bipyramidal geometry.98 There R4 R1 R2 R3 R4
OH MeCN, 1% H2O
is a similar interaction between [Ph4 Bi]+ and an oxygen R3
atom of an acetate ligand in [Ph4 Bi][Ph2 Bi(O2 CCF3 )2 ]. (28)
Pentaphenyl bismuth is Lewis acidic and will react Ph
with pyridine to give the adduct BiPh5 pyridine or with OH OH
Ph4BiO2CCF3 + BTMG
LiPh in diethyl ether or THF to produce unstable
Li[BiPh6 ].105 or Ph3BiCl2 + NaH
Organobismuth(V) reagents are useful for a wide variety (29)
of organic transformations including transfer reactions, O O
oxidation of primary, secondary, benzylic, and allylic CO2Et CO2Et
Ph4BiO2CCF3 (30)
alcohols (equations 24 33). Copper or copper salts promote, Ph
and may be required for, the transfer reactions.106,107 BTMG
BISMUTH: ORGANOMETALLIC CHEMISTRY 11
Ph3BiCl2
R1
BiPh3
2
R
+ 2NaCl
Scheme 4
O O O O R R R R R R
Ph3BiCl2
(31) 2NaH Ph3BiCl2
BTMG
OEt OEt Na+2 or
Ph Ph H2 O O O O
O O Ph3BiO
H H BiPh3
O O (26)
Ph4BiCO3 Ph Ph (32)
Ph Ph RCH=SO2
OH Ph4BiX O R R
(33)
BiPh3 +
O O
The compound Ar2 Bi(O)OMe, which was prepared via O2S
the reaction of Ar3 Bi and 4-MeC6 H4 SO2 NClNa, has been R
reported to acylate amides, thioamides, ureas, and thioureas.
The first step of the process is believed to be reaction of Scheme 5
the Ar2 Bi(O)OMe compound with acetic acid to replace the
methoxide with acetate.110 The ylide function is exchanged upon addition of dimethyl
sulfide in the presence of CuCl to give R1 R2 CSMe2 and BiPh3
3.3 Bismuth Ylides (Scheme 5). Exchange could also be accomplished to PPh3
and AsPh3 but not SbPh3 . The sodium salt of acetylacetone
Bismuth ylide chemistry is not nearly so well developed reacts with Ph3 BiCl2 to generate an ylide complex that could
compared to the extensive chemistry of phosphorus ylides not be isolated. Attempts at chromatography led to the iso-
(R3 P=CR2 ). This is in large part due to the inaccessibility lation of the C-phenylated acetylacetone instead. This ylide
of bismuth alkyl cations R4 Bi+ for deprotonation to ylides, complex, however, reacts with H2 CSO2 generated in situ to
as is frequently the strategy employed for phosphorus. A give 1,3-oxathiole-3,3-dioxide.
theoretical investigation of the group 15 ylides predicted In related chemistry, BiPh3 is oxidized by anhy-
that the formation of MeBiH3 + from MeCl and BiH3 drous chloramine-T (RSO2 NClNa, R = p-MeC6 H4 ) or with
is endothermic.111 Quaternization of bismuth is difficult, Rf SO2 NH2 (R = CF3 , 4-FC6 H4 , CF2 CF2 CF2 CF3 ) in the pres-
but MeO3 SCF3 will react with BiMe3 to give BiMe4 + .95 ence of NaOMe to give Ph3 Bi=NSO2 R.114 This may be
Alternative routes that involve the reaction of sodium compared to the same reaction carried out in the presence
salts of methylene compounds with Ph3 BiCl2 or Ph3 BiO of wet methanol, which gives the Ar2 Bi(O)OMe complexes
(Schemes 4 and 5) have been developed.107,112 In many described above.
cases, the bismuthonium ylides have not been isolated from
solution. Compound (26), where R = Me, has yielded to X-
ray structural characterization.113 The BiCylide distance is 4 RELATED ARTICLES
2.16 A, only slightly shorter than the BiCphenyl distances,
suggesting that there is considerable ionic character in the Antimony: Organometallic Chemistry; Arsenic: Organo-
Bi ylide bond. arsenic Chemistry; Bismuth: Inorganic Chemistry.
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16 BISMUTH: ORGANOMETALLIC CHEMISTRY
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Bonding Energetics of enantioselective reduction of olefins and ketones developed
by Noyori et al. (see Asymmetric Synthesis by Homogeneous
Catalysis),28,29 the ring-opening and closing metatheses of
Organometallic olefins reported by Grubbs et al. (see Organic Synthesis Using
Compounds Metal-mediated Metathesis Reactions),3032 or the recently
developed ruthenium-catalyzed synthesis of formic acid and
formamides in supercritical CO2 .33,34
Reto Dorta & Steven P. Nolan In order to gain insight into the thermodynamics of phos-
University of New Orleans, New Orleans, LA, USA phine binding to ruthenium systems, the tetrameric complex
(Cp RuCl)4 was chosen as the starting material (see Polynu-
clear Organometallic Cluster Complexes). Complexes of
the type Cp Ru(diene)Cl are formed from the tetrameric
1 Introduction 1 (Cp RuCl)4 compound according to equation (1)35,36 and pro-
2 Case Studies 1 vide a thermodynamic entryway into the solution calorimetric
3 Closing Remarks 17 studies of ligand substitution in these systems. Table 1 gives
4 Related Articles 18 an overview of the enthalpies of substitution for the reaction in
5 References 18 equation (1) and shows that for subsequent ligand substitution
chemistry involving phosphines and arsines, the relatively
labile nature of the COD ligand in Cp Ru(COD)Cl is ideal.
THF
(Cp RuCl)4(s) + 4diene(soln) 4Cp Ru(diene)Cl(soln) (1)
30 C
1 INTRODUCTION
Indeed, reacting this complex with monodentate arsine/ph-
During the last 10 years, significant advances have been osphine/phosphite ligands provides access into the thermo-
made in the area of organometallic bonding energetics. Most chemistry of the ligand substitution of equation (2). Table 2
data were obtained from solution calorimetric studies. In gives the respective enthalpies of ligand substitution found by
the present chapter, a compilation of thermochemical data on calorimetry for the series of monodentate phosphine ligands.
organometallic systems is presented. This account represents a
survey and is by no means exhaustive yet we have endeavored THF
to provide the reader with as much data as possible in an effort Cp Ru(COD)Cl(soln) + 2L(soln) Cp Ru(L)2 Cl(soln) + COD(soln)
30 C
to complement the contribution found in the first edition.
(2)
Table 1 Enthalpies of substitution (kcal mol1 ) for equation (1) Table 3 Enthalpies of substitution (kcal mol1 ) in the reaction:
140
PMePh2 Ligand). Since Cp is less electron donating than Cp , the Cp
PEt3 system is able to accommodate greater electron density from
130 Pn Bu3 the incoming two-electron donor (higher electrophilicity),
PPhMe2 therefore leading to more exothermic enthalpies of ligand
120
PMe3
150
110
P(OMe)3 PPh3
140
Phosphine cone angle (q)
PMePh2
100 Pn Bu3
15 20 25 30 35 40
130 PEt3
H of reaction (kcal mol1)
120 PPhMe2
Figure 1 Enthalpy of reaction vs phosphine cone angle for a
series of tertiary phosphine ligands in the Cp Ru(PR3 )2 Cl system PMe3
(slope = 1.94; R = 0.93) 110
P(OMe)3
monodentate phosphine and arsenic ligands have also been 100
measured in order to examine how the overall steric and 20 25 30 35 40 45
electronic variations accompanying this change in ancillary H of reaction (kcal mol1)
ligation (Cp versus Cp) influence the thermodynamic stability
of Cp Ru(PR3 )2 Cl (with Cp = Cp or Cp ). Again, the Figure 2 Enthalpy of reaction vs phosphine cone angle for a
reactions of CpRu(COD)Cl with a series of phosphines have series of tertiary phosphine ligands in the CpRu(PR3 )2 Cl system
been found to be quantitative and rapid under the experimental (slope = 1.95; R = 0.91)
BONDING ENERGETICS OF ORGANOMETALLIC COMPOUNDS 3
substitution. One of the best ways to experimentally assess Table 6 Enthalpies of substitution (kcal mol1 ) in the reaction:
the lack of phosphine electronic factors playing a role in these
THF
two systems is to determine the bond dissociation enthalpies Cp Ru(COD)Cl(soln) + 2L(soln) Cp Ru(L)2 Cl(soln) + COD(soln)
30 C
of a series of isosteric, para-substituted triphenylphosphine
ligands. The enthalpies of reaction of Cp Ru(COD)Cl (where
Cp = Cp and Cp ) with several para-substituted monodentate L Complex Hrxn Cp a
phosphines are listed in Table 4. This study clearly indicates AsEt3 Cp Ru[AsEt3 ]2 Cl 15.0 (0.2)
an important lack of sensitivity associated with the enthalpies PPh3 Cp Ru[PPh3 ]2 Cl 18.1 (0.2)
of ligand substitution reactions as a function of electronic P(p-CF3 C6 H4 )3 Cp Ru[P(p-CF3 C6 H4 )3 ]2 Cl 20.7 (0.2)
variation and can only be explained in terms of overwhelming P(p-CIC6 H4 )3 Cp Ru[P(p-CIC6 H4 )3 ]2 Cl 21.7 (0.4)
P(p-CH3 OC6 H4 )3 Cp Ru[P(p-CH3 OC6 H4 )3 ]2 Cl 21.8 (0.4)
steric contribution to the enthalpy of reaction.
P(p-FC6 H4 )3 Cp Ru[P(p-FC6 H4 )3 ]2 Cl 22.0 (0.5)
Besides the class of traditional phosphines ligands, the Pn Bu3 Cp Ru[Pn Bu3 ]2 Cl 26.0 (0.2)
related class of phosphite ligands has been utilized as P(O-o-MeC6 H4 )3 Cp Ru[P(O-o-MeC6 H4 )3 ]2 Cl 26.0 (0.2)
ancillary ligation in various industrially relevant processes PEt3 Cp Ru[PEt3 ]2 Cl 27.2 (0.2)
such as the hydrocyanation (see Hydrocyanation) of PPh2 Me Cp Ru[PPh2 Me]2 Cl 29.4 (0.2)
P(OPh)3 Cp Ru[P(OPh)3 ]2 Cl 31.2 (0.2)
dienes or hydroformylation (see Hydroformylation) or the P(OCH2 )3 CEt Cp Ru[P(OCH2 )3 CEt]2 Cl 31.6 (0.2)
copolymerization of CO and olefins.38,39 The thermochemistry PPhMe2 Cp Ru[PPhMe2 ]2 Cl 31.8 (0.3)
of ligand substitution of a variety of phosphite ligands has PMe3 Cp Ru[PMe3 ]2 Cl 32.2 (0.4)
P(Oi Pr)3 Cp Ru[P(Oi Pr)3 ]2 Cl 32.7 (0.3)
P(OMe)3 Cp Ru[P(OMe)3 ]2 Cl 37.5 (0.4)
Table 5 Enthalpies of Substitution (kcal mol1 ) in the reaction:
a
THF
Enthalpy values are reported with 95% confidence limits.
CpRu(COD)Cl(soln) + 2L(soln) CpRu(L)2 Cl(soln) + COD(soln)
30 C
PMePh2
n
P Bu
P(Oi Pr)3
130 PEt3
130
P(OPh)3
120 PPhMe2
120
PMe3
110
110
P(OMe)3
P(OCH2)3CEt P(OMe)3
100
100 20 25 30 35 40 45
32 34 36 38 40 42
H of reaction (kcal mol1)
H of reaction (kcal mol1)
150
P(p-XC6H4)3 (4)
150 PPh3 P(NC4H8)3
P(O-o-MeC6H4)3 P(NC4H4)3 P(NC4H4)2Ph
Phosphine cone angle (deg)
140
Phosphite cone angle (q)
140 PMePh2
P(Oi Pr)3 PEt3
130 130 Pn Bu3
P(OPh)3 PPhMe2
120 120
PMe3
110
P(OCH2)3CEt P(OMe)3 110
P(OMe)3
100
26 28 30 32 34 36 38
H of reaction (kcal mol1) 100
15 20 25 30 35 40
H of reaction (kcal mol1)
enthalpies involved in this correlation are directly related to one involving chloride ligation and a comparison of the results
RuP bond dissociation enthalpies, Figure 7 is in fact a bond is shown in Table 8.
length-relative bond dissociation enthalpy correlation. The Important comparisons can be made between the Cp RuCl
correlation between crystalline RuP distances and solution and the Cp Ru(OCH2 CF3 ) systems and show that enthalpies
thermochemical measurements suggests that longer bonds are of reaction involving similar phosphine ligands are more
associated with less exothermic reactions (dmpm > PMe3 > exothermic for the Cp RuCl moiety. This trend is understood
PPhMe2 > PPh2 Me > PEt3 > Pn Bu3 > PPh3 ). to reflect the increased electron donation residing on the
As mentioned above, the ancillary Cp (see Cyclopentadie-
nyl) ligands (Cp versus Cp ) can influence the enthalpies of
(Cp*Ru OCH2CF3)2
reaction of Cp RuCl systems with phosphorous ligands. The
availability of [Cp Ru(OCH2 CF3 )]2 ,41,42 permits therefore H1 H3
a direct comparison of alkoxide vs chloride ancillary +2PR3 +4PR3
ligands in this system. The enthalpies of reaction of
[Cp Ru(OCH2 CF3 )]2 with PR3 (PR3 = PCy3 , Pi Pr3 ) have H2
Cp*Ru(PR3)OCH2CF3 CpRu(L)2OCH2CF3
been measured by solution calorimetry giving complexes +4PR3, 2PR3
[Cp Ru(PR3 )(OCH2 CF3 )] and in order to test the internal
consistency of the approach, a thermochemical cycle, shown PR3 PR3 H1 H2 H3
in Scheme 1, was constructed leading to the formation of PCy3 PEt3 18.9 (0.3) 41.6 (0.6) 60.1 (0.5)
Cp Ru(PR3 )2 (OCH2 CF3 ). This reactivity is analogous to the PCy3 P(OMe)3 18.9 (0.3) 65.8 (0.8) 83.8 (0.8)
PiPr3 PEt3 18.6 (0.2) 43.6 (0.8) 60.1 (0.5)
2.35 PiPr3 P(OMe)3 18.6 (0.2) 67.2 (0.8) 83.8 (0.8)
P(n Bu)3
2.34
P(Ph)3
RuP bond distance ()
2.32
PMe(Ph)2
Scheme 1
P(Et)3
2.31
Table 8 Relative average RuPR3 bond disruption enthalpies
2.30
P(Me)2Ph P(Me)3 (kcal mol1 ) in the reaction:
2.29 Cp RuX + nL Cp Ru(L)n X n = 1,2
dmpm
2.28
22 24 26 28 30 32 34 L Complex X = ORf a X = Cla
H of reaction (kcal mol1) Pi Pr3 Cp Ru[Pi Pr3 ]X 6.5 (0.3) 9.4 (0.3)
PCy3 Cp Ru[PCy3 ]X 6.7 (0.3) 10.5 (0.2)
PEt3 Cp Ru[PEt3 ]2 X 14.3 (0.5) 18.4 (0.6)
Figure 7 Plot of the RuP bond distance (A) vs the enthalpies P(OMe)3 Cp Ru[P(OMe)3 ]2 X 20.2 (0.8) 23.8 (0.4)
of reaction (kcal mol1 ) for the Cp Ru(L)2 Cl complexes (slope =
2.48; R = 0.97) a
Enthalpy values are reported with 95% confidence limits.
6 BONDING ENERGETICS OF ORGANOMETALLIC COMPOUNDS
metal when the ancillary ligand X is (OCH2 CF3 ), leading to the destabilizing strain energy caused by steric and torsional
a tendency of the Cp Ru(OCH2 CF3 ) moiety to be able to forces present in the metallacyclic fragment.
accept less electron density from the incoming donor ligands, The enthalpies of ligand substitution for these chelating
resulting in a lower exothermic value for the enthalpy of ligands are presented in Table 9.
reaction. Several trends are worth noting: (1) reactions of alkyl-
substituted phosphines prove to be more exothermic; (2) ring
strain is present in the four- and seven-membered ring
2.2 Binding of Chelating Diphosphine Ligands
systems. For this latter trend, a relative comparison of all the
to Cp-ruthenium Systems
data of these chelating diphosphines with the corresponding
Chelating diphosphine ligands (see Chelating Lig- monophosphines shows that the strain energy for the seven-
ands) have been widely used in organometallic chemistry membered metallacycle is smaller than for the four-membered
and are especially indispensable ligand systems in analogue; (3) similar to the trend seen for monophosphines,
enantioselective catalytic transformations (see Asymmetric the Cp ligand system shows an increased exothermicity in
Synthesis by Homogeneous Catalysis).28 With the com- enthalpies of reaction.
plex Cp Ru(COD)Cl (Cp = Cp and Cp ) at hand, solution Analogous to the studies with monodentate phosphorous
thermochemical investigations of ligand substitution involving ligands, a thermochemical study of ligand substitution involv-
chelating diphosphines can be carried out, giving complexes ing diphosphine compounds with weak -donor and strong
of the type Cp Ru(PP)Cl. It might be predicted that a major -acceptor character involving the recently reported ligands
factor influencing the metal diphosphine complex reactivity Ph2 PNMeNMePPh2 , (PhO)2 PNMeNMeP(OPh)2 , (C4 H4 N)2
and stability must involve the metal ligand enthalpy term. PCH2 CH2 P(NC4 H4 )2 , and ((EtO2 C)2 C4 H2 N)2 PCH2 CH2
This bond disruption enthalpy (BDE) value can be viewed as P[NC4 H2 (CO2 Et)2 ]2 was undertaken.43 The results in
a sum of the stabilizing metal phosphorous interaction and Table 10 (for Cp and Cp ) clearly suggest that steric factors
THF
CpRu(COD)Cl(soln) + P P(soln) CpRu (P P)Cl(soln) + COD(soln)
30 C
Hrxn a Hrxn b
P P
dppm 19.4 (0.2) 19.4 (0.2)
Ph2P PPh2
dmpm 23.8 (0.3) 26.2 (0.2)
Me2P PMe2
dppb 24.7 (0.3) 30.1 (0.3)
Ph2P PPh2
dppe 29.8 (0.2) 30.5 (0.2)
Ph2P PPh2
dppp 30.7 (0.2) 32.4 (0.2)
Ph2P PPh2
dppv 31.3 (0.2) 32.7 (0.2)
Ph2P PPh2
depe 35.6 (0.3) 39.4 (0.3)
Et2P PEt2
dmpe 34.8 (0.2) 39.7 (0.3)
Me2P PMe2
a
Enthalpies of reaction for the Cp -based system which are reported with 95%
confidence limits. b Enthalpies of reaction for the Cp-based system also reported
with 95% confider limits.
BONDING ENERGETICS OF ORGANOMETALLIC COMPOUNDS 7
PP Hrxn Cp a Hrxn Cp a
[(EtO2 C)2 C4 H2 N]2 PCH2 CH2 P[NC4 H2 (CO2 Et)2 ]2 24.0 (0.4) 19.4 (0.2)
(C4 H4 N)2 PCH2 CH2 P(NC4 H4 )2 29.1 (0.1) 23.2 (0.4)
Ph2 PNMeNMe PPh2 29.7 (0.4) 22.6 (0.2)
Ph2 PCH2 CH2 PPh2 30.5 (0.2) 29.8 (0.2)
(PhO)2 PNMeNMe P(OPh2 ) 32.4 (0.3) 26.4 (0.2)
Ph2 PCHCHPPh2 32.7 (0.2) 31.3 (0.2)
Et2 PCH2 CH2 PEt2 26.0 (0.2) 35.6 (0.3)
Me2 PCH2 CH2 PMe2 39.7 (0.3) 34.8 (0.2)
a
Enthalpy values are reported with 95% confidence limits.
predominate in all these cases, but at least some electronic weakest RuPR3 bond yet investigated and relative bond
effects must be present in minor extend, with reaction disruption enthalpies were established and are shown in
enthalpies markedly lower than for basic diphosphines. Table 11. As observed for smaller phosphines, the steric
factors have a profound influence on the enthalpy of
reaction and a direct relationship between the two can be
2.3 Binding of Sterically Demanding Phosphine Ligands established.
to Cp-ruthenium Systems
THF
Sterically demanding phosphine ligands play an important (Cp RuCl)4(s) + 4PR3(soln) 4Cp Ru(PR3 )Cl(soln) (4)
30 C
role in organometallic chemistry in helping to stabilize very
PR3 = PCy3 ; Hrxn = 41.9 0.2 kcal/mol
reactive species and play crucial roles in several catalytic
systems such as the very successful ruthenium-alkylidene PR3 = Pi Pr3 ; Hrxn = 37.4 0.3 kcal/mol
catalysts reported by Grubbs et al. (see Organic Synthesis THF
Using Metal-mediated Metathesis Reactions).30,31 Direct Cp Ru(PR3 )Cl(soln) + 2PR3(soln) 4Cp Ru(PR3 )2 Cl(soln) + PR3
30 C
solution calorimetric measurement of the relative donating
PR3 = PCy3 , Pi Pr3 ;
properties of large cone-angle phosphines would therefore be
highly desirable and have not been reported. The reaction of PR3 = phosphines with smaller (5)
(Cp RuCl)4 with sterically demanding monodentate tertiary
phosphine ligands leads to rapid and clean formation of the
unsaturated Cp Ru(PR3 )Cl (where PR3 = Pi Pr3 or PCy3 ),44 2.4 Phosphine Exchange in a Ruthenium-Alkylidene
and is therefore amenable to such an investigation (equation 4). System
Furthermore, the very reactive nature of these unsaturated The utilization of neutral 16-electron ruthenium-alkylidene
complexes can be exploited in order to thermodynamically complexes as olefin metathesis catalysts (see Organic
link the Cp Ru(PR3 )Cl to the Cp Ru(PR3 )2 Cl systems Synthesis Using Metal-mediated Metathesis Reactions) has
discussed earlier according to equation (5). The results show had a tremendous impact in both organic and polymer
that these two sterically demanding phosphines exhibit the chemistry.45,46 These complexes of type (PR3 )2 Cl2 Ru=CR2
(Where PR3 = sterically demanding phosphine) have been
Table 11 Relative bond disruption enthalpies (kcal mol1 ) in the thoroughly investigated, especially with regard to the role
following reaction played by the phosphine ligands.47 Yet, this understanding
THF is based principally on kinetic studies and thermochemical
(Cp RuCl)4(soln) + nL(soln) 4Cp Ru(L)n/4 Cl(soln)
30 C investigations are highly desirable. In fact, complex
(PPh3 )2 Cl2 Ru(=CC=CPh2 )30 constitutes an ideal entryway
L Complex n Relative BDEa into the thermochemistry of these ruthenium-carbene species
Pi Pr3 Cp Ru(Pi Pr3 )Cl 4 9.4 (0.3) insofar as PPh3 replacement by a series of sterically demanding
PCy3 Cp Ru(PCy3 )Cl 4 10.5 (0.2) tertiary phosphine ligands can be investigated by batch
Pn Bu3 Cp Ru(Pn Bu3 )2 Cl 8 18.1 (0.4) calorimetry. This transformation and a list of all reaction
PEt3 Cp Ru(P Et3 )2 Cl 8 18.4 (0.6) enthalpies is provided in Table 12. With these data at hand,
P(OMe)3 Cp Ru(P(OMe)3 )2 Cl 8 23.8 (0.4)
the interpretation of these enthalpies of ligand substitution in
a
Relative BDE values were derived by dividing the enthalpy value terms of phosphine steric and electronic parameters according
by the number of RuPR3 formed during the reaction of interest. to equation (3) (see above) shows that an excellent correlation
8 BONDING ENERGETICS OF ORGANOMETALLIC COMPOUNDS
PR3 Hrxn a
PPh3 145 13.45 0
PBz3 165 10.3 1.3 (0.2)
PCyPh2 153 9.4 1.8 (0.2)
PCy2 Ph 162 5.35 3.8 (0.2)
Pi Bu3 143 5.7 3.8 (0.2)
Pi Pr3 160 3.45 5.2 (0.1)
PCy3 170 1.4 6.5 (0.3)
a
Enthalpy values are reported with 95% confidence limits.
2070 14
PPh3 PPh3
2068 12
Electronic parameter (cm1)
PBz3
2066 PBz3
PCyPh2 10
PCyPh2
2064
8
c
2062
PCy2Ph
PCy2Ph 6
2060 P i Bu3 Pi Bu3
PPr3
4
2058
PCy3 PCy3 Pi Pr3
2
2056
7 6 5 4 3 2 1 0 1
H of reaction (kcal mol1) 0
7 6 5 4 3 2 1 0 1
H of reaction (kcal mol1)
9 PCy3 Pi Pr3
characterizing this class of ligands. They cannot be viewed
8 Pi Bu3 in the same light as phosphine ligands since a cone angle
PCy2Ph (as defined by Tolman37 ) cannot be defined in the present
7 system. As a first model to describe the steric parameters
6 of NHCs and of phosphines, the amount of volume of a
sphere centered on the metal, buried by overlap with atoms of
5 PCy2Ph
various NHC ligands, %VBur , was measured.15 The volume
4
PBz3 of this sphere would represent the space around the metal
atom that must be shared by the different ligands upon
3 coordination. Of course, the bulkier the specific ligand, the
PPh3
2
larger the amount of that sphere will be occupied by the
7 6 5 4 3 2 1 0 1 ligand, that is, greater %VBur . A graphical representation
H of reaction (kcal mol1) of this geometrical analysis is reported in Figure 11 and
a compilation of %VBur values is presented in Table 14.
When the experimental BDEs are plotted versus %VBur , a
Figure 10 Enthalpy of phosphine exchange reaction (kcal mol1 ) vs
linear relationship is found to exist, not unlike the linear
pKa of HPR3 + for trans-(PR3 )2 Cl2 Ru=CHCH=CPh2 complexes.
(slope = 1.092; R = 0.983). Solid: literature value.16 Hollow: relationships found for BDEs versus phosphine cone angle
predicted value in the corresponding Cp Ru(PR3 )Cl and Cp Ru(PR3 )2 Cl
(Figure 12). This simple model is only a starting point to
understand the steric requirements of ligand classes other than
Table 13 Enthalpies of substitution (kcal mol1 ) and relative
RuNHC bond disruption enthalpies (kcal mol1 ) in the reaction:
THF
(Cp RuCl)4(s) + 4L(soln) 4Cp Ru(L)Cl(soln)
30 C
Relative
L Hexp
a
BDEb
the chlorides in the backbone act as electron-withdrawing Table 14 Steric parameters associ-
groups when compared to H in IMes. ITol is a slightly better ated with selected NHC and sterically
donor than IpCl, a trend that is again in line with electron- demanding PR3 ligands
donating/withdrawing abilities of arene substituents.55 Substi- Ligand %VBur
tuting an aryl group for an alkyl increases the donor ability of
the carbene ligand. The case in point is the ICy, which is some ITol 23
5.6 kcal mol1 more exothermic than IMes. Finally, IAd is the IMes 26
SIMes 27
least exothermic ligand examined and steric effects are at the IPr 28
origin of this low enthalpy of ligand substitution. SIPr 29
With the crystallographic data of complexes Cp Ru(IMes) Pi Pr3 32
Cl, Cp Ru(SIMes)Cl, Cp Ru(IPr)Cl, Cp Ru(SIPr)Cl, Cp Ru PCy3 32
(ITol)Cl, and Cp Ru(IAd)Cl at hand, and knowing the IAd 37
10 BONDING ENERGETICS OF ORGANOMETALLIC COMPOUNDS
40 trans-RhCl(CO)(PZ3 )2 + 2PZ 3
trans-RhCl(CO)(PZ 3 )2 + 2PZ3
P(NC4H4)3
(6)
35
P(NC4H4)2Ph2
P(p-CIC6H4)3 P(p-FC6H4)3 that is, where substitution is favored in the case of good
15 -acceptors/weak -donors. Such a system was found in the
PPh3 P(p-CH3OC6H4)3
case of the chelating tridentate bis(phosphino)-amido ligands
10 P(p-CH3C6H4)3 RPNP (Fryzuks ligand).58,59 Substitution of cyclooctene in
5 [RPNP]Rh(COE) with phosphines (or CO) was investigated
by solution calorimetry and shows conclusively and con-
0 vincingly that better acceptor ligands give the more stable
25 30 35 40 45 50 55 60 65
complexes in the [RPNP]RhL system (Table 16). An analysis
H of reaction (kcal mol1) for the reactions of both complexes supports the notion that
the observed trends, although opposite, are electronic in nature
(all the phosphine ligands being isosteric) and a good corre-
Figure 14 Electronic parameter ( ) vs enthalpies of reaction
(kcal mol1 ) for the RhCl(CO)(PR3 )2 system (slope = 1.05; lation was found for the reaction enthalpy versus Tolmans
R = 0.96) electronic parameter ( ) (Figure 16).
These results thus illustrate the importance of reorgani-
zation energies in thermodynamic analyses of metal ligand
H Protonation of PR3 Ligand (kcal mol1)
H (kcal mol1 )
20 25
a d e
(Pi Pr3 )2 RhCl(soln) + C8 H16 O(soln)
18 b 20
c
C7 H16(g) + CO(g) C8 H16 O(g) 3.3 0.5
16 d 15 (Pi Pr3 )2 RhCl(soln) + CO(g)
c
(Pi Pr3 )2 Rh(CO)(Cl)(soln) 39.3 0.7 (8)
14 10
Figure 16 Reaction enthalpy vs Tolmans electronic param- (Pi Pr3 )2 RhClH2 (soln) + But NC(soln) (Pi Pr3 )2 Rh(CNBut )(Cl)(soln)
eter ( ) for rhodium systems: circles = [i PrPNP]RhL;
+ H2 H = 9.9 0.4 kcal mol1 (9)
diamonds = trans-RhCl(CO)L2 . Letters correspond to the ligands
L = PPh3 (a), PPh2 pyrl (b), PPhpyrl2 (c), Ppyrl3 (d), and Ppyrl3 (e) 0.5[(Pi Pr3 )2 RhCl]2 (soln) +But NC(soln) (Pi Pr3 )2 Rh(CNBut )(Cl)(soln)
H = 33.5 0.5 kcal mol1 (10)
2.7 Addition Reactions to a Rhodium-phosphine System 0.5 [(P Pr3 )2 RhCl]2 (soln) + H2(g)
i
2.7.1 Thermodynamics of CO Addition (Pi Pr3 )2 RhCl(t BuNC)(soln) H2 = 33.5 (0.5) kcal mol1 (13)
0.5 [(Pi Pr3 )2 RhCl]2(soln) + L(soln) (Pi Pr3 )2 RhCl(L)(soln) (14)
In order to avoid problems associated with calorimetric
H3 = H2 H1
measurements with a gas-phase reactant, the following
reactions (equation 7) were exploited to determine the L H3 (kcal mol1 )
enthalpy of equation (8). The enthalpy of equation (8) is N2 7.6 (0.7)
C2 H4 15.9 (0.6)
subsequently determined using the available thermodynamic PhCCPh 13.6 (0.7)
BONDING ENERGETICS OF ORGANOMETALLIC COMPOUNDS 13
0.5[(Pi Pr3 )2 RhCl]2(soln) + PhCCPh(soln) developed and utilized a fluorinated ligand that allows for
(P Pr3 )2 RhCl(PhCCPh)(soln) H = 14.2 (0.4) kcal mol
i 1
(15)
biphasic segregation of a catalyst from the organic reactants
and products.6062 The synthesis of this ponytail ligand,
P[CH2 CH2 (CF3 )5 CF3 ]3 , and the synthetic strategies employed
2.7.4 Thermodynamics of the Addition of Aldehydes for obtaining a series of fluorinated phosphine ligands
and acyl Chlorides with more tunable stereoelectronic properties are shown in
equations (18 20).
Thermodynamic studies of the enthalpy of addition of
aldehydes and acyl chlorides to [Rh(Pi Pr3 )2 Cl]2 and the AIBN
hypothetical monomer Rh(Pi Pr3 )2 Cl gave unsaturated five- PH3 + 3CH2 CH(CF2 )5 CF3 P(CH2 CH2 (CF2 )5 CF3 )3 (18)
coordinate Rh(III) compounds according to equations (16) THF
R2 PCl + Rf OH R2 PORf + HNEt3 Cl (19)
and (17) and afforded the values shown in Table 17. NEt3
0.5 [(Pi Pr3 )2 RhCl]2(soln) + RCHO(soln) R = Rf O, i Pr, Ph, Cy; Rf = CH2 CH2 (CF2 )5 CF3
Et2 O
(Pi Pr3 )2 RhClH[C(O)R](soln) (16) R2 PCl + Rf MgI R2 PRf + MgICl (20)
0.5 [(Pi Pr3 )2 RhCl]2(soln) + RC(O)Cl(soln) R = Cy, Pr; Rf = CH2 CH2 (CF2 )5 CF3
i
2000
Table 17 Enthalpy of addition of XY to PPh2ORf
[(Pi Pr3 )2 RhCl]2 (Hrxn ) and the hypothetical 1990
monomer (Pi Pr3 )2 RhCl (Hmin ) in solution
(kcal mol1 ) 1980
1970 PCy2ORf Pi Pr2ORf
XY Hrxn Hmin
1960
H2 23.6 (0.6) 32.5
C8 H17 CHO 15.2 (0.3) 24.1 1950
70 68 66 64 62 60 58 56
PhCHO 10.8 (0.4) 19.7
(p-Tol)CHO 10.5 (0.4) 19.4 H of reaction (kcal mol1)
(p-CF3 C6 H4 )CHO 12.7 (0.4) 21.6
(p-MeOC6 H4 )CHO 10.5 (0.3) 19.4
C8 H17 C(O)Cl 24.6 (0.3) 33.5 Figure 17 Carbonyl stretching frequency (cm1 ) vs enthalpies of
PhC(O)Cl 21.7 (0.3) 30.6 reaction (kcal mol1 ) for the RhCl(CO)(PR3 )2 system (slope = 5.47;
R = 0.96)
14 BONDING ENERGETICS OF ORGANOMETALLIC COMPOUNDS
A measure of the steric parameter associated with that N2 O typically donates an oxygen atom to reducing agents,
the widely used fluorous tertiary phosphine ligand thereby liberating dinitrogen. One might therefore have pre-
P[CH2 CH2 (CF2 )5 CF3 ]3 was obtained by measuring the reac- dicted the reaction between Mo(N[R]Ar)3 and nitrous oxide
tion enthalpies for ligand substitution of this ligand and to occur according to equation (24).
Cp Ru(COD)Cl (Cp = Cp and Cp). As discussed earlier,
these two systems exhibit a marked dependence on steric O
parameters and by simple interpolation of the enthalpy reac- N
tion value of the phosphorous ligand (equation 22), they can N(R)Ar N2O
be inserted into the linear relationship existing between the Ar(R)N Mo Mo
N(R)Ar Ar(R)N N(R)Ar
cone angle and the enthalpy of reaction. Respective values
of 134 (from Cp data) and 127 (from Cp data) and an Ar(R)N
(23)
average value of 130 4 were obtained for the Tolman steric +
parameter of P[CH2 CH2 (CF2 )5 CF3 ]3 . N
THF Mo
Cp Ru(COD)Cl + 2PRf 3 Cp Ru(PRf 3 )2 Cl + COD (22) Ar(R)N N(R)Ar
30 C
soln soln soln soln Ar(R)N
H = 34.7 (0.3)kcal mol1 , Cp = Cp
O
H = 26.1 (0.3)kcal mol1 , Cp = Cp N(R)Ar N2O
Ar(R)N Mo Mo
N(R)Ar N2 Ar(R)N N(R)Ar
2.9 Reactivity of a Molybdenum System Ar(R)N
relevant to the selective splitting of the nitrous oxide NN that the calorimetrically determined MoN BDE for nitride
bond by complex [Mo]. N2 O splitting reaction as well as the [Mo]-N is the first such value to be so obtained, and it is
NO and O binding reactions were particularly amenable to of interest further in that it indicates that the splitting of
analysis by solution calorimetry because of their rapid and N2 by 2 equiv of complex (1), giving 2 equiv of [Mo]-
essentially quantitative nature. N, is favored enthalpically by ca. 86 kcal mol1 and serves
as a driving force for N2 cleavage by complex (1). The
O [Mo]-O BDE was also determined and was found to be
N(R)Ar ONC5H5 155.6 1.6 kcal mol1 , a value equal to F /2 in Figure 18.
Ar(R)N Mo Mo
N(R)Ar
This fact, taken in conjunction with the knowledge that the
Ar(R)N N(R)Ar
NN-O BDE value is 40 kcal mol1 , permits the conclusion
Ar(R)N
that the conversion of 2 equiv of complex [Mo] to 2 equiv of
(25) [Mo]-O (if effected by 2 equiv of N2 O) would be downhill
O by a quantity equal to G, that is 231.2 3.2 kcal mol1 .
Since the latter value is in excess of the value of D by
N
N(R)Ar
107.4 4.0 kcal mol1 , one sees that oxidation of complex
NO [Mo] by nitrous oxide giving Mo(O)(N[R]Ar)3 would have
Ar(R)N Mo Mo
N(R)Ar Ar(R)N N(R)Ar been vastly preferable to NN bond splitting, the pathway
Ar(R)N that prevails evidently for reasons that are entirely kinetic in
origin.
(26)
The enthalpies of these reactions were measured and 2.10 Binding of Phosphines to a Platinum System
the results are shown in Figure 18. NO binding to [Mo]
gives C, the enthalpy of which is found to be 82.5 Platinum(II) complexes of the type (COD)PtRX (COD =
2.5 kcal mol1 , while the N2 O splitting reaction is indicated 4 -1,5-cyclooctadiene; R, X = alkyl, aryl, halide) are
as D, the corresponding enthalpy change being 123.8 known for many combinations of R and X, and their
0.8 kcal mol1 . As an aside, the latter two values in reaction chemistry is well developed (see Platinum:
combination with A, the 114 kcal mol1 literature value for Organometallic Chemistry).66 The lability of the CODPt
the NNO bond dissociation enthalpy,65 yield the value B interaction renders these compounds convenient sources of
for the MoN BDE of 155.3 3.3 kcal mol1 . It appears organoplatinum fragments for coordination to Lewis bases
such as phosphines, according to equation (27). In an effort
to better understand the factors that influence the stability of
2[Mo] + N + NO + N2O bis(phosphine)platinum(II) species, a thermodynamical study
100 of the reaction in equation (27) was undertaken for a series
2O + 2N2 + 2 [Mo] of monodentate and bidentate phosphine ligands of varying
A
50 steric and electronic character.
E B
2[Mo]O + 2N2
250
2.10.1 Monodentate Phosphine Ligands
30
Hrnx a PMePh2
H (kcal mol1)
Complex (P P) Ligand (kcal mol1 ) 28
20
2.10.2 Bidentate Phosphine Ligands
28
Enthalpy of ligand substitution in the
CpRu(PP)CI system (kcal mol1)
30
dppe dppb
dppp 3 CLOSING REMARKS
32
dppv
34 As can be seen above, a significant portion of the recent
36 advances in the area of organometallic thermodynamics has
been achieved using solution calorimetric methods. This is
38
dmpe
not to say that other techniques have not been successfully
depe
40 used to obtain data on such systems. Other methods include
experimentally determined bond energy terms by mass
42
38 36 34 32 30 28 26 spectrometry,75,76 and a large number of DFT calculations7780
Enthalpy of ligand substitution in the PtMe2(PP) have been reported.
system (kcal mol1)
Ligand substitution, oxidative addition reaction, and
absolute bond enthalpies afford insight into thermody-
Figure 21 Enthalpy of ligand substitution in the CpRu(PP)Cl namic driving forces behind important processes. One
system and PtMe2 (PP) systems (slope = 1.1; R = 0.96) of the most striking among the examples given above
18 BONDING ENERGETICS OF ORGANOMETALLIC COMPOUNDS
is the markedly increased donor ability of NHC versus 11. J. Shen, E. D. Stevens, and S. P. Nolan, Organometallics, 1998,
trialkylphosphines, experimentally determined by solution 17, 3000.
calorimetry and the stability/reactivity consequences that 12. M. E. Cucullu, C. Li, S. P. Nolan, S. T. Nguyen, and
follow in ruthenium-based olefin metathesis (see Alkene R. H. Grubbs, Organometallics, 1998, 15, 5565.
Metathesis). There remains a great deal of work to be 13. D. C. Smith, C. M. Haar, L. Luo, C. Li, M. E. Cucullu,
performed in the area of organometallic thermodynamics. C. H. Mahler, S. P. Nolan, W. J. Marshall, L. N. Jones, and
The importance of metal ligand bond energetics cannot P. J. Fagan, Organometallics, 1999, 18, 2357.
be overstated, yet the physical organometallic chemist has
14. J. Huang, H. J. Schanz, E. D. Stevens, and S. P. Nolan,
so far played a catch-up role to rapidly moving areas of
Organometallics, 1999, 18, 2370.
organometallic chemistry and catalysis. The predictive pow-
ers of such data are beginning to be realized, yet more 15. A. C. Hillier, W. J. Sommer, B. S. Yong, J. L. Peterson,
data are needed in order to guide synthetic and catalytic L. Cavallo, and S. P. Nolan, Organometallics, 2003, 22, 4322.
chemistries. 16. K. Wang, A. S. Goldman, C. Li, and S. P. Nolan, Organometal-
lics, 1995, 14, 4010.
17. K. Wang, T. J. Emge, A. S. Goldman, C. Li, and S. P. Nolan,
Organometallics, 1995, 14, 4929.
4 RELATED ARTICLES 18. K. Wang, G. P. Rosini, S. P. Nolan, and A. S. Goldman, J. Am.
Chem. Soc., 1995, 117, 5082.
Asymmetric Synthesis by Homogeneous Catalysis; 19. S. A. Serron, S. P. Nolan, and K. G. Moloy, Organometallics,
Carbonylation Processes by Homogeneous Catalysis; 1996, 15, 4301.
Hydrocyanation by Homogeneous Catalysis; Iridium: 20. C. Li, S. P. Nolan, and I. T. Horvath, Organometallics, 1998,
Organometallic Chemistry; Mechanisms of Reaction of 17, 452.
Organometallic Complexes; Multi-Heme Cytochromes 21. C. M. Haar, J. Huang, S. P. Nolan, and J. L. Peterson,
& Enzymes; Organic Synthesis Using Metal-mediated Organometallics, 1998, 17, 5018.
Metathesis Reactions; Platinum: Organometallic Chemistry; 22. J. Huang, C. M. Haar, S. P. Nolan, W. J. Marshall, and
Polynuclear Organometallic Cluster Complexes; Rhodium: K. G. Moloy, J. Am. Chem. Soc., 1998, 120, 7806.
Organometallic Chemistry; Ruthenium: Organometallic
23. D. C. Smith, E. D. Stevens, and S. P. Nolan, Inorg. Chem.,
Chemistry.
1999, 38, 5277.
24. D. C. Smith, E. D. Stevens, S. P. Nolan, W. J. Marshall,
K. G. Moloy, A. Prock, and W. P. Giering, Organometallics,
1999, 18, 474.
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Borates: Solid-state feature leads to a variety of unusual structural arrangements
that are not found with any other homonuclear polyoxoanion.
Chemistry These arrangements appear extensively, both in anhydrous and
hydrated crystals. In fact, many of the large-scale applications
of metal borates involve use of hydrated forms. Because the
Douglas A. Keszler chemistry and technology of these materials have recently
Oregon State University, Corvallis, OR, USA been reviewed,2,3 they will not be considered here. Instead,
only those characteristics that are unique to anhydrous borates
will be discussed.
1 Introduction 1
2 Electronic Structure 1
3 Crystal Structure 2 2 ELECTRONIC STRUCTURE
4 Synthesis 6
5 Optical Properties 7
6 Individual Borates 9 2.1 Triangular and Tetrahedral Units
7 Related Articles 9
8 References 9 A wide range of borate structures contain the isolated
triangular BO3 3 group (1), while a fewer number contain
the isolated tetrahedral BO4 5 group (2). The triangular group
tends to be quite symmetrical with OBO angles near 120
Abbreviations and a BO distance near 1.375 A4 that varies as the sum of the B
and appropriate O crystal radii. The tetrahedral group exhibits
BBO = -BaB2 O4 ; LBO = LiB3 O5 . individual OBO angles in the range 95.7 119.4 (mean
value = 109.4 ) and individual BO distances from 1.373
to 1.699 A (mean value = 1.47 A); exaggerated distortions
from the triangular and tetrahedral geometries have been
compiled.5
1 INTRODUCTION
3 5
O O O
Borates are unique among the oxoanion compounds of the B B
second-row elements in forming anhydrous substances that O O O O
are both chemically and thermally stable. These characteristics
(1) (2)
provide a ready accessibility to a large number of synthetic
examples that have widespread use. While the borate
minerals, precursors to synthetic borates, comprise only a The occurrence of triangular versus tetrahedral coordina-
small percentage of the Earths crust (see Boron: Inorganic tion in a particular compound may be addressed by considering
Chemistry), concentrated deposits in the United States, the information available on the electronic structures of each
Turkey, Russia, Argentina, and China have provided an group. The atomic charge distributions in these groups have
economical source of materials for exploitation. The overall commonly been approximated with one of two extreme for-
demand for borates in the US for 1993, as measured by malisms: the purely covalent Formal Charge model or the
B2 O3 content, is anticipated to be near 400 000 t.1 More purely ionic Oxidation Number model. In the triangular unit
than 50% of this total is used for manufacturing glass, and the formal charge of each O atom is 1 and that of the B
approximately 25% is used for fiber glass insulation. In other atom is 0; these values sum to the overall oxoanionic charge
applications, alkali metal borates are active as herbicides, of 3. In the tetrahedral unit the formal charge of each O
insecticides, fertilizers, and detergents, and high quality borax atom remains 1, but that of the B atom is reduced to 1;
(Na2 B4 O7 10H2 O) is employed in electrolytic capacitors and again these values sum to the overall charge, now 5. The
by the nuclear industry. Selected materials find use in powder oxidation numbers in both borate groups are 2 for the O
and single-crystal form as high-end optical components. atoms and +3 for the B atom, and appropriate overall charges
Crystalline metal borates, like silicates, have a rich for each group are produced. The charges assigned with the
structural chemistry that extends from the simple orthoanions formal-charge model emphasize the strong polarizing power
to their condensation into complex rings, chains, networks, of the B3+ ion and the covalent interactions that result from
and frameworks. Unlike the fixed coordination number of four overlap of B and O orbitals having the same principal quan-
for the Si atom in silicates, however, the coordination number tum number (n = 2). This model, however, fails to portray the
of the B atom in borates can be either three or four. This unique considerable polarity of the BO bond that results from the
2 BORATES: SOLID-STATE CHEMISTRY
significant Electronegativity difference ( = 1.5) between in metal atoms that form binary acidic oxides contain a higher
the B and O atoms. This particular aspect is emphasized in concentration of BO4 groups. These trends are demonstrated
the oxidation-number model. Considering the BO interaction with examples in Section 3. In terms of Crystal Field Theory,
in the context of a composite model, a small positive charge the higher charge of the BO3 groups also generates stronger
should be associated with the B atoms in both the triangular crystal fields at the associated metal sites; examples of this
and tetrahedral units and a small negative charge with the O effect are given in Section 5.
atoms; orbital overlap then produces a polar covalent bond.
Such a description is consistent with the electron population
analysis of the X-ray diffraction data from the mineral Kernite6
(Na2 B4 O6 (OH)2 3H2 O) and the results of molecular orbital 3 CRYSTAL STRUCTURE
calculations (see Molecular Orbital Theory).7
The known structural chemistry of anhydrous borates
3 through 1985 has been summarized,11 and those borate
O
minerals containing fused octahedra and triangles have been
B classified according to selected fundamental building blocks.12
O O
(3)
3.1 Structures with Isolated Triangular Groups
the noncentrosymmetric trigonal form of the mineral Huntite, Figure 3 Chain structure of STACK compounds A6 MM (BO3 )6 . M
CaMg3 (CO3 )4 , but other forms are known where the packing atoms are indicated with open bonds and M atoms with filled bonds
of the BO3 groups within the planes is again modified to
afford centrosymmetric structures having lower symmetry. Example formulations are Sr6 HoFe(BO3 )6 (A = Sr, M = Ho,
Derivatives containing each of the lanthanides have been M = Fe), Ba6 GdSc(BO3 )6 (A = Ba, M = Gd, M = Sc), and
reported for the Al and Ga compounds, but only those Sc Sr3 Sc(BO3 )3 (A = Sr, M = Sc, M = Sc).
compounds containing the lanthanides La, Ce, Pr, Nd, Sm, The structure is characterized by chains formed from a
Eu, and Gd exist. Apparently, the large size of the Sc atom series of M- and M -centered distorted octahedra that are
produces a Scborate matrix with a trigonal prismatic site that
stacked one atop the other and separated by BO3 groups
is too large to be stabilized by the smaller lanthanides.
(Figure 3). By virtue of their connectivity to the A atoms, the
On the basis of the coordination environments of the metal
octahedra are crystallographically and chemically dissimilar;
atoms in this structure type, it is difficult to rationalize the
the M-centered octahedron is larger than the M -centered site.
existence of the family. The six-fold coordination at the Ln
As a result, larger cations preferentially occupy the M site and
site is small for a lanthanide atom (see Coordination Numbers
smaller cations the M site. These octahedra are bridged by
& Geometries and Scandium, Yttrium & the Lanthanides:
intervening A atoms in nine-coordinate AO9 sites. Although
Inorganic & Coordination Chemistry). It might be anticipated
the structure may be portrayed with this chain description, the
that the stoichiometric combination LaSc3 (BO3 )4 would be
rich A concentration and high density of AO9 interconnections
more thermodynamically stable as a mixture of the separate
actually produce a fully three-dimensional arrangement of
phases 3ScBO3 + LaBO3 where the coordination number of
the atoms.
the La atom in LaBO3 is nine. The stability of the Huntites
must then be associated with a higher coordination number
for the O atoms. As noted above, the coordination number of 3.2 Oligomeric and Polymeric Condensation of
the O atoms in the calcite structure of ScBO3 is three, but Triangular Groups
in the Huntite structure this number is four. The higher
number and the attendant increased metalO interactions Like MOM linkages in complex oxoanions of the heavier
provide the stability for the existence of the family. The congeners of Groups 14 and 15 (see Phosphates: Solid-state
compound LaSc3 (BO3 )4 does undergo the peritectic reaction Chemistry), BOB couplings result in the formation of higher
LaSc3 (BO3 )4 LaBO3 + 3ScBO3 above 1550 C. order polyanions. The simplest condensation of BO3 units
The STACK family13 of compounds provides an example affords the pyroborate group (4). In this group the terminal
of a simple orthoborate structure type where the BO3 BO distances tend to be somewhat longer than the bridg-
groups do not pack in such readily perceived planes. These ing BO distances, and a wide variation (111.8 180 ) in the
compounds are characterized by the formula A6 MM (BO3 )6 bridging BOB angle is observed. Although illustrated here
where A = Sr or Ba, and M and M = any cation of formal as a planar group, a considerable range of interplanar angles
charge +2, +3, or +4 that occupies an octahedral site. With between the terminal BO2 groups has been reported; the angle
more than 125 known derivatives, these compounds form varies from 0 in the compound Sr2 Sc2 B4 O11 14 to the nearly
one of the larger structural families of solid-state oxides. orthogonal angle of 84 in the compound Ba5 (B2 O5 )2 F2 .15
4 BORATES: SOLID-STATE CHEMISTRY
O
B
O O O O O
B B B B B
O O O O O O O
Figure 4 Polyhedral representation of the polyborate anion in the
(6) (7) compound LiB3 O5 . BO4 tetrahedra are lightly shaded, and BO3
triangles are deeply shaded, here, and in Figures 5 7
believed to produce the four-coordinate B atom (equation 1). arises from the excited 2 E or 4 T2 state. With its sharp line
emission, ruby (Cr3+ :Al2 O3 ) is an example of a Cr3+ laser
operating on the basis of 2 E emission. Because this emission
OR OR
occurs primarily in the zero-phonon lines, the ruby laser
LiOR + B Li+ RO B (1)
operates as a three-level system with a rather high threshold
RO OR OR
RO for oscillation.
In the late 1970s, Cr3+ -doped alexandrite (BeAl2 O4 ) was
To form gels in this mixed alcohol solvent system, a found to lase on the vibrational sideband of the 4 T2 4
A
critical value of N4 must be exceeded. This observation transition. Because this transition terminates on vibrationally
has been rationalized on the basis of the kinetic stability excited states of the ground level, the laser operates as a four-
of BOB bonds toward hydrolysis or alcoholysis. Because level system with a much lower threshold. Several similar
tetrahedrally coordinated borate groups are coordinatively Cr3+ lasers were subsequently developed.36 A limitation in all
saturated (see Coordinative Saturation & Unsaturation), this these systems, however, arises from the 4 T2 4
T1 a excited
group is unable to participate in dissociative reactions of the state absorption which overlaps to some extent the 4 T2 4
A2
triangular group that hinder polymerization and the formation emission. Materials exhibiting higher excited state absorption
of gels (equation 2). cross sections and greater overlap with the emission band are
found to be less efficient lasers. Examples of Cr3+ laser crystal
R
systems with low excited state absorption losses (and therefore
O H high laser efficiency) are emerald, and the aforementioned
OR OH
hosts BeAl2 O4 and LiCaAlF6 .
Because excited state absorption losses are generally
ROH + B O B B O B B B
+ higher for those materials that emit at longer wavelengths,
(2)
the compound Sr3 Sc(BO3 )3 was synthesized as a host for
A sufficient N4 is required to give at least one tetrahedrally shorter wavelength emission.37 This compound contains BO3
coordinated B atom as a connection between the oligomeric triangles and a high concentration of the basic oxide SrO that
structural units. Comparison of FTIR spectra of gels with those in combination produce a relatively strong crystal field at the
of molecular and crystalline alkali-metal borates indicates that Cr3+ dopant site. Luminescence from the doped host at room
the initial polyborate species to emerge during hydrolysis are temperature is centered in a broad band at 750 nm (cf. 810 nm
in Cr3+ :ScBO3 ), representing a considerable blue shift that
units composed of six-membered rings. Additional hydrolysis
could lead to an increased lasing efficiency. As a host, the
is associated with condensation reactions between these rings.
material is similar to alexandrite in that transitions from both
Since N4 must be >0.23 for formation of stable gels, a 2
E and 4 T2 levels are observed at room temperature.
network of BO3 and BO4 groups has been proposed for the
The huntite Nd:YAl3 (BO3 )4 has also been lased.38 This
lithium borate polymers near the gel point.
crystal has generated interest because, as noted in Section 3,
it is noncentrosymmetric and can also function as an
optical frequency converter. This host can then self-double
the 1064-nm emission line of the Nd3+ ion directly to
5 OPTICAL PROPERTIES 532 nm, eliminating the need for separate laser and frequency
conversion crystals. With diode pumping, the crystal provides
a compact source of green light. Because the Nd3+ ion
5.1 Laser Materials
absorbs near the doubled frequency, the dopant concentration
must be near 4% to achieve an efficient production of green
Broad-band laser emission has been observed from Cr3+ -
light.
doped ScBO3 .35 The luminescence band extends from 700
to 1000 nm, with a peak at 810 nm. This emission is a
vibrationally assisted transition from the excited 4 T2 level 5.2 Nonlinear Optical Materials
to the ground 4 A level of the Cr3+ ion (see Ligand Field
Theory & Spectra). The centrosymmetric symmetry of the Crystals of BBO39 and LBO40 are extensively used for
dopant site affords a relatively long fluorescence lifetime of generating visible and UV light from high-power pulsed
115 s. The laser tuning range is 787 892 nm, and the laser lasers. The general utility of the materials derives from their
pumped output efficiency is near 29%. This value may be high optical damage thresholds and transparency ranges that
compared to the high efficiencies of 51% for Cr3+ :BeAl2 O3 extend to 190 nm for BBO and 170 nm for LBO.
and 52% for Cr3+ :LiCaAlF6 . The second-order susceptibility of LBO (deff = 0.7 pm
Cr3+ laser emission has been obtained from a variety of V1 ) for doubling 1064-nm light from a Nd:YAG laser is
crystals in two very different ways, depending on the strength approximately 40% of that of BBO (deff = 2.0 pm V1 ).
of the crystal field at the dopant site and whether the emission These susceptibilities have been modeled by summing the
8 BORATES: SOLID-STATE CHEMISTRY
5.3 Phosphors
ne
The doped compounds Ce3+ ,Tb3+ :GdMgB5 O10 , and
Ce ,Mn2+ :GdMgB5 O10 are used as phosphors41 in efficient
3+
Figure 8 Packing of the cyclic metaborate rings in the structure of fluorescent lamps having a high color rendition index (see
-BaB2 O4 Luminescence). The host is isostructural to the compound
BORATES: SOLID-STATE CHEMISTRY 9
LaMgB5 O10 which was described in Section 3. In this struc- 6.2 BaLnB9 O16 (Ln = lanthanide)47
ture the Mg-centered distorted octahedra share vertices with
the Gd-centered sites, and the Gd-centered environments fuse The host BaGdB9 O16 exhibits a quantum efficiency = 0.65
by sharing edges. The high efficiencies of these materials when doped with the ion Eu3+ . Eu2+ emission from the same
derive from the efficient transfer of energy from one ion to host is characterized by a broad band peaking in the blue
the next.42 The Ce3+ dopant effectively absorbs the 254-nm at 460 nm. Structural data for these compounds have not
been reported.
light of the Hg emission in the fluorescent lamp. The emission
band of this ion is at a sufficiently high energy to provide
for the complete transfer of excitation energy to the Gd3+ 6.3 LiBGeO4 and LiSiGeO4 48
ions. In the Tb3+ -doped material the energy migrates through
the Gd3+ sublattice until it encounters a Tb3+ center, where These mixed oxides have been considered as nonlinear
energy transfer (Gd3+ Tb3+ ) results in the production of optical materials (see Nonlinear Optical Materials).49 They
green light at 545 nm. In the Mn2+ compound the ion sub- crystallize as ordered derivatives of the cristobalite structure.
stitutes on the Mg2+ site. Similar energy-transfer steps lead As early X-ray structural studies were performed on twinned
crystals grown from congruent melts, their true symmetry was
to the production of red light characterized by a broad-band
not firmly established. Untwinned single crystals have been
emission centered at 620 nm.
produced by hydrothermal methods, and the space group has
Two important characteristics, one electronic and one
been convincingly established as I4.
structural, contribute to the success of these materials.
The weak crystal field produced by the polyborate at the
Ce3+ ion leads to a high-energy emission and a significant
overlap between the Ce3+ relaxed excited state and Gd3+ 7 RELATED ARTICLES
absorption bands, allowing efficient energy transfer from Ce3+
to Gd3+ . Also, the linkage of the metal atom coordination Oxides: Solid-state Chemistry; Sol Gel Synthesis of
environments provides a pathway for energy migration Solids.
through the Gd sublattice to the luminescent ions.
The phosphor Tb3+ :InBO3 has been promoted as a green
phosphor in cathode-ray tubes and as a possible scintillator.43
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25. W. J. Dell, P. J. Bray, and S. Z. Xiao, J. Non-Cryst. Solids, 41. T. Welker, J. Lumin., 1991, 48 & 49, 49.
1983, 58, 1. 42. G. Blasse, Phys. Stat. Sol. (A), 1982, 73, 205.
26. L. N. Demyanets, Prog. Cryst. Growth Charact. Mater., 1991, 43. J. P. Chaminade, A. Garcia, M. Pouchard, C. Fouassier,
21, 299. B. Jacquier, D. Perret-Gallix, and L. Gonzalez-Mestres, J.
27. V. Nikolov and P. Peshev, J. Solid State Chem., 1992, 96, 48. Cryst. Growth, 1990, 99, 799.
28. B. H. T. Chai, M. Gualtieri, and M. H. Randles, Proc. 44. L. Shirong, H. Qingzhen, Z. Yifan, J. Aidong, and C. Chen,
SPIE Int. Soc. Opt. Eng., 1988, 968, 69. Acta Crystallogr., Sect. C, 1989, 45, 1989.
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31. P. A. Morris, in Materials for Nonlinear Optics, Chemical
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Washington, DC, 1991, Vol. 455, p. 380. 6, 659.
Borides: Solid-state tendency toward the formation of boron boron bonds as
the boron/metal ratio increases. The electron deficiency of
Chemistry boron is also of major importance in the theories of bonding
and band structure of the borides.
Binary borides are formed with transition and inner
Torsten Lundstrom transition elements, with alkali and alkaline-earth elements,
Uppsala University, Uppsala, Sweden and with the p elements, aluminum, and silicon. In addition,
a group of more electronegative elements (C, O, P, S, As, Se)
form compounds with boron, which display properties and
structures closely related to those of some borides. This group
1 Introduction 1 of compounds is also briefly described in the present article as
2 Occurrence and Crystal Chemistry of Borides 1 well as the polymorphs of elemental boron.
3 Synthesis 7
4 Band Structure and Bonding 9
5 Properties and Applications 9
6 Related Articles 11
7 References 11 2 OCCURRENCE AND CRYSTAL CHEMISTRY OF
BORIDES
a. Transition Elements
ScB2 TiB V3 B 2 o-,t-Cr2 Ba o-,t-Mn2 B Fe23 B6 -meta Co3 B Ni3 B
ScB12 Ti3 B4 VB Cr5 B3 h,l-MnB Fe3 B-meta Co2 B Ni2 B
ScB19 TiB2 V5 B 6 h,l-CrB Mn3 B4 Fe2 B CoB o-Ni4 B3
V3 B 4 Cr3 B4 h-MnB2 FeB m-Ni4 B3
V2 B 3 Cr2 B3 MnB4 NiB
VB2 CrB2
CrB4
YB2 ZrB2 Nb3 B2 Mo2 B Tc3 B Ru7 B3 Rh7 B3 Pd5 B
YB4 ZrB12 NbB h,l-MoB Tc7 B3 Ru11 B8 Rh5 B4 Pd3 B
YB6 Nb5 B6 MoB2 TcB2 RuB RhB Pd5 B2
YB12 Nb3 B4 MoB2.3 Ru2 B3 Pd2 B
YB25 Nb2 B3 Mo1x B3 RuB2
YB50 NbB2
YB66
LaB4 Hf B Ta2 B W2 B Re3 B OsB IrB0.9 Pt4 B
La1x B6 Hf B2 Ta3 B2 h,l-WB Re7 B3 Os2 B3 IrB1.1 Pt2 B
hp-Hf B12 TaB WB2 ReB2 OsB2 IrB1.35 PtB0.7
Ta5 B6 W2 B5x
Ta3 B4 W1x B3
TaB2
b. Main Group Elements
B 2 H6 b
LiB Be4 B B B4 C B12 N2 B12 O2 BF3
Li3 B14 Be2 B (homogeneity range BN hp-B2 O
-Be2 B3 B4.3 C-B9 C) BO
BeB2 B 2 O2
BeB3 B 2 O3
BeB6 BO2
BeB9 12 BO3
Na3 B20 MgB2 AlB2 SiB2.8 B12 P2 B12 S2 B2 Cl4
Na2 B29 MgB4 -AlB12 SiB6 BP BS BCl3
NaB15 Mg2 B14 -AlB12 B2 S2
B2 S3
BS2
KB6 CaB6 B12 As2 B12 Se2 BBr3
BAs BSe
B2 Se3
BSe2
SrB6 BI3
BaB6
a
Notations: o = orthorhombic, t = tetragonal, h,l = high, low temperature, meta = metastable, hp = high pressure. b and
higher boranes.
In addition to the phases of Table 1, there are a large systems without any ternary phase at all, for instance, the
number of lanthanide and actinide borides crystallizing in system LaCuB.
the structure types of AlB2 , Sm2 B5 , ThB4 , CaB6 , ScB19 , It is very often difficult to establish the existence and
UB12 , YB25 , YB50 , and YB66 . A total of more than 200 composition of borides owing to one or more of the following
binary borides have been reported until now. More or less reasons. The great reactivity of boron toward, for instance,
complete binary phase diagrams of most of the systems of the crucible material leads to the occurrence of impurities
Table 1 are available11 with the exception of those of the in the products. The impurities are often said to stabilize
alkali metals. a structure type, while in reality a ternary compound has
A total of more than 700 ternary borides have been been formed although unintentionally. It is also difficult
prepared and characterized.3,5,6,8 Most of these phases occur to analyze chemically or by microprobe the boron content
in the RETB systems. A maximum of 12 ternary phases owing to low accuracy of the methods. Indeed, in many
has, for instance, been found in each of the SmCoB and cases a single crystal-structure determination is, together
CeCoB systems6 (see Figure 1). There are also ternary with complementary structural information obtained by other
BORIDES: SOLID-STATE CHEMISTRY 3
2.2.1 Modifications of Elementary Boron 2.2.2 Solid Solutions of Transition Elements in -rh. Boron
The existence of three crystalline and one amorphous The boron modifications are semiconductors. -rh. boron
modification of boron has been established (Table 2). is a high-temperature semiconductor with a band gap of
Reports on further modifications are unreliable and refer 1.5 eV. The transition elements and some p elements (C,
to uncharacterized and/or impurity stabilized material. -tetr. Si) form solid solutions in -rh. boron.10 In this manner, the
boron, also denoted tetr. I boron (a = 8.75 A, c = 5.06 A), electrical characteristics are changed (doping). The maximum
solid solubility varies with solute and can be as high as 4
to 5 atomic percent. The well-known difficulties to prepare
Table 2 Crystallographic data for the boron modifications ultra-pure -rh. boron is partially due to the solid solutions
that most of the elements form with boron.
Unit cell dimensions
The structure of the solid solutions is very complex.
Modification Space Group a(A) c(A) Investigations have shown that partial (and only partial)
occupancies of up to five interstitial atomic positions occur.
-rh. boron21 R3m 4.927(3) 12.564(7)
These atomic positions are situated between the icosahedra of
-rh. boron22 R3m 10.930(1) 23.815(3)
-tetr. boron18 P 41 or P 43 10.14(1) 14.17(1) the structure. In a few cases a substitutional mechanism for the
solid solubility has been demonstrated, similar to the silicon
BORIDES: SOLID-STATE CHEMISTRY 5
substitution for boron in the structure of B2.89 Si, which has four boron atoms occur in the structure types of W3 CoB2
the ideal composition B6 Si.23 and Mo2 IrB2 , respectively. Distorted prisms are common
among ternary compounds containing large and small metal
atoms. Chain fragments can also occur as a consequence of
2.2.3 Borides with Isolated Boron Atoms boron defects.
Infinite boron zig zag chains with BB distances 1.65
Following Rogl,8 we distinguish three subgroups among the to 1.90 A and bond angles of 115 are found in the
borides with isolated boron atoms, namely, metal framework structure types of FeB, CrB, and MoB. The boron coordination
structures, substitutional metal borides, and proper metal is trigonally prismatic with two boron atoms and one
boride structures. The metal framework structures include metal atom situated outside the rectangular faces. There
elemental or binary compound types, which are stabilized are a large number of binary and ternary representatives
by boron atoms filling the voids of the metal host lattice. of these and other related structure types. Double and
Examples of such structures are the -borides (Hf9 Mo4 B), the triple chains characterize the structure types Ta3 B4 and
-borides (mostly ternary M21 M2 B6 phases), and the Cu3 Au- V2 B3 , respectively. Single and double chains occur in
type phases (Ni3 InB0.15 ), with prismatic, antiprismatic, and the structure type of V5 B6 . In the ternary structures of
octahedral coordination of the metal atoms around the boron Cr2 AlB2 and Cr3 AlB4 , single and double boron chains,
atoms, respectively. respectively, occur together with CsCl-type units. Branched
In substituted metal borides, the boron atoms replace boron chains are found in the Ru11 B8 structure and also
partially or completely, in an ordered or disordered manner, in the UBC structure with carbon atoms branching off the
metal atoms in the structure. Structure types belonging to zig zag boron chain. Chains or fragments of chains also
this subgroup are, for instance, two structural series based occur in borocarbides of many structure types, for instance,
on the substitution of boron for small metal atoms in the Sc2 BC2 .19
intermetallic structure types CaCu5 and MgZn2 , respectively. Studies of borides with the composition RT4 B4 are very
The structural relationship is nicely demonstrated in the rewarding to clarify the interplay between superconductivity
series CaCu5 CeCo3 B2 ErIr3 B2 ErRh3 B2 . Another and magnetism. A large number of RT4 B4 compounds have
very important structure type belonging to this subgroup is that been reported with T = Fe, Co, Ru, Rh, Os, and Ir and with
of Nd2 Fe14 B, a compound which displays excellent permanent RE comprising nearly all rare-earth metals. The compounds
magnetic properties. In the structure of the Nd2 Fe14 B, crystallize in at least six structure types, namely, CeCo4 B4 ,
the boron atom has a trigonal prismatic environment of LuRh4 B4 , LuRu4 B4 , NdCo4 B4 , YOs4 B4 , and Ce1+x Fe4 O4
metal atoms. In addition, there is a close correspondence of tetragonal or orthorhombic symmetry. Another group of
between the metal arrangement of Nd2 Fe14 B and the boron-containing materials of interest for superconductivity
intermetallic -phase. Thus this structure is also closely and magnetic studies are quaternary borocarbides of
related to the metal framework structures already discussed. composition RETBC, for instance, LuNi2 B2 C, LuNiBC,
The substitutional metal borides include approximately 30 and Lu2 NiBC2 . A review was published in 2000.20
structure types.
The proper metal boride structures with isolated boron
atoms include approximately 20 structure types with many 2.2.5 Borides with Two-dimensional Boron Networks
ternary representatives. The boron coordination is trigonal
prismatic (in the Fe3 C, Ti3 P, Re3 B Th7 Fe3 structure types), Many borides in the composition range B/Me 1.5 to 2.5
octahedral (in Rh5 B4 ), or Archimedian prismatic (in the crystallize with various stacking sequences of metal layers
CuAl2 -type structure with many M2 B representatives). and boron layers.8 Ordered or disordered defects often occur
in the layers. Most of the structures belonging to the AlB2
structure family24 can be described by the stacking sequence
2.2.4 Borides with Chains and Fragments of Chains of planar or puckered boron and metal layers as shown in
Figure 5. The common, simple hexagonal AlB2 structure is,
In o-Mn2 B (earlier denoted Mn4 B) and t-Mn2 B (CuAl2 for instance, described by the sequence AHAH. . . and the
type), a tendency toward chain formation is observed, although structure of W2 B5x by AHAKBHBH. . ., where the K
the BB distance in the structures is relatively large, namely, boron layers are slightly puckered. Orthorhombic stacking
2.1 A, as compared 1.8 A (0.1 A) in normal chains. In these variants, for instance, RuB2 and IrB1.35 , also belong to this
structures, the metal surrounding of the boron atom consists structure family. Mo1x B3 (x small) is a relatively boron-rich
of an Archimedian or a distorted Archimedian antiprism. A compound built up of defective metal layers (every third atom
closer contact between the boron atoms of about 1.8 A is, is lacking) and H type layers occurring in AlB2 . It is noticeable
however, brought about when trigonal prismatic coordination that MgB2 , belonging to the simple AlB2 -type structure, is
polyhedra of the boron atoms share rectangular faces. Chain a superconductor with Tc as high as 39 K.25 The supercon-
fragments consisting of boron pairs occur in Cr5 B3 and in V3 B2 ducting properties of MgB2 were not discovered until 2001
(U3 Si2 -type structure). Chain fragments consisting of three or although the compound was synthesized already in the 1950s.
6 BORIDES: SOLID-STATE CHEMISTRY
A,B,C H H
K K
Re
Figure 5 Layers of metal atoms (A, B, C), planar boron layers (H, B
Y
H ), and puckered boron layers (K, K ), occurring in the AlB2 and Y2ReB6
related type structures
X
B1
B3
X
B2
suitable for industrial production. The methods for preparation 3.5 Fused-salt Electrolysis
of borides may be classified as follows.
Electrolysis is carried out at 1000 to 1300 K of a mixture
of alkali halide, metal oxide, and a borate. This is a process
3.1 Direct Combination of the Elements of industrial interest. However, high-purity and single-phase
products are not easily obtained.
Direct reaction of the elements is carried out under vacuum
or inert gas by melting or by reaction sintering at a temperature
below the melting point. The melting procedure is often 3.6 Preparation of Coatings by Chemical Vapor
associated with the crucible problem, which is pronounced at Deposition (CVD)
high temperature.24 The metal boron melt invariably attacks
In Chemical Vapor Deposition (CVD), the gaseous
oxide ceramics, in particular, boron-rich compositions, and
reactants are carried over a heated substrate, where the
to avoid impurities or stabilization effects from such attacks,
chemical reactions or thermal decomposition occur.35 If the
levitation melting or cold crucible techniques (for instance,
process parameters are correctly selected an adherent solid
arc melting) are preferable, in particular for the highest
coating is obtained with attractive mechanical or electrical
temperatures. Boron nitride is an excellent crucible material
properties. Overall reactions can be of the type already
for boron-rich compositions at not too high temperatures.
mentioned in Section 3.2.
Synthesis can be difficult owing to high volatility of the
metals and/or their reactivity toward oxygen (alkali, alkali-
3.7 Crystal Growth
earth, and rare-earth metals), which requires a sealed crucible
technique and high vacuum or inert gas atmosphere. Crystal growth of boride phases can be carried out by
most of the methods known. However, the high melting
3.2 Reduction of a Metal Oxide and Boron Halide with points and the great reactivity of, in particular, boron-rich
Hydrogen compounds limits the techniques applicable and calls for
special equipment. The low-temperature, gas-phase methods
A mixture of, for instance, metal and boron halides is (1300 1600 K), including CVD and chemical vapor transport,
reduced at temperatures of 1300 to 1600 K. Borides of Ti, Zr, have been used for crystal growth of diborides, especially
and Hf have been prepared according to: TiB2 , ZrB2 , and TaB2 with melting points around 3300 K.
Liquid phase methods (crystal pulling, floating zone melting,
MCl4 (g) + 2BCl3 (g) + 5H2 (g) MB2 (s) + 10HCl(g) (1)
and flame fusion) are used to produce diboride, hexaboride,
and REB66 single crystals.35,36
Adherent coatings of diborides can also be obtained by thermal
An attractive method to produce single crystals (in the
decomposition of boron halides.
dimension range from m to several mm) is the high-
temperature solution (flux) method, because of its simplicity
3.3 Reduction of a Metal Oxide or Other Metal and the low temperature required.37 The elements are dissolved
Compound Using B, C or Boron Carbide in the solvent metal (often Al) and subsequently the solution
is slowly cooled to room temperature. A prerequisite is, of
The borothermic process for diborides proceeds in vacuo course, that the solubility of the used solvent in the desired
at high temperature (>1300 K) according to the equation: boride is insignificant. The solubility of Al in most boron-
Mn Om (s) + (2n + m) B(s) n MB2 (s) + 1/2m B2 O2 (g) (2) rich binary borides has been found to be extremely small.
Crystals prepared in this manner are suitable for measurement
It can be used for hexaborides as well. Reduction with boron of physical properties, for instance, microhardness, electrical
carbide can also be used for diborides as well as hexaborides, resistivity, and so on.
although in that case alkaline-earth and rare-earth hexaborides
will dissolve some carbon forming RB6x Cx borocarbides. 3.8 Other Methods
temperature increase and triggered self-sustaining reaction bonding) along the ZrB directions. At the Fermi level
(exothermic), respectively. the states are nearly completely of Zr-4d character. These
calculations are in qualitative, and in some cases in very
good quantitative, agreement with experimental data for ZrB2
from X-ray photoemission spectroscopy, measurements of
4 BAND STRUCTURE AND BONDING optical properties, Hall effect, dc resistivity, and specific heat.
Experimental and theoretical studies indicate a relatively small
The nature of the chemical bonding in borides was in transfer of electrons from metal to boron.40 Band structure
early work described by simplified models emphasizing the calculations of the new medium-Tc superconductor MgB2 (Tc
role of MM, MB, and BB bonding. The question of 39 K) and related diborides have been published.41 It was
magnitude and direction of charge transfer has been much early suggested to use a rigid band model for the electronic
debated. There is complete agreement that the bonding structure of the diborides and only one DOS curve, which
in borides involves simultaneous contributions of metallic, was then filled up with the number of electrons available in
covalent, and ionic bonding to the cohesive energy. The the boride. This method has often proved to be a very crude
proportions, however, depend on the nature of the metallic approximation.
component and the boron/metal ratio. In recent years, the In early studies of hexaborides, the conclusion was reached
growth of more powerful experimental methods and greatly that there is a finite energy gap between the conduction and
improved calculation facilities have contributed immensely to valence bands and that the valence band contains 20 electrons.
our knowledge of band structure and bonding in borides. The six boron atoms provide 18 electrons and, if the metal
Several band structure calculations (see Electronic is divalent (Ca, Br, Ba), the hexaboride is anticipated to be
Structure of Solids) for diborides have been carried out.38,39 insulating (semiconducting), while a higher valence, occurring
The density of state versus energy for ZrB2 from a self- among the rare-earth elements, is anticipated to lead to metallic
consistent calculation is shown in Figure 10. The Figure conductivity. This is in agreement with experiments. The
demonstrates a Fermi level (EF ) at the minimum of the simple picture involves a charge transfer to the boron network
DOS curve between bonding states (left) and antibonding and thus a significant ionicity in the bond. A self-consistent
states (right). It is difficult to draw conclusions from symmetrized APW calculation of the energy band structure
the corresponding band structure (not reproduced here), of LaB6 42 has revealed many more details. The calculated
although the authors suggest covalent bonds within the density of states for the valence bands agrees well with X-ray
boron layers and some covalency (perhaps also metallic photoelectron measurements. The LaB bonding originates in
the strong hybridization of La-d states and d-like B-sp states
of the six octahedral boron atoms.
A simple treatment of the stability requirements of a boron
icosahedron in a solid was presented early.1 An icosahedral
boron cluster was shown to require two external electrons.
The icosahedron is linked to its neighbors via normal covalent
1
bonds. This description leads to a simple understanding of the
stability of the B6 O and B6 P structures.
The electronic structure of quaternary borides of the type
States/ (eV cell)
the handbook contains values of mechanical and refractory 64 MGOe, which is more than twice than that of the very
properties. More recent fundamental data can be found in the strong SmCo5 magnets.
proceedings from the boron symposia,1216 and specialized Most borides are chemically inert in bulk form, which
textbooks.46 Values for some physical properties of a few has led to industrial applications as engineering materials,
borides are collected in Table 4. principally at high temperature. The transition metal borides
Table 4 displays a broad range of resistivities beginning display a considerable resistance to oxidation in air. A
with the insulator h-BN, continuing with the semiconductors few examples of applications are given here. Titanium and
CaB6 , B4 C, and YB66 , and ending with the metallic phases zirconium diborides, alone or in admixture with chromium
Fe2 B, TiB2 , and LaB6 . The resistivity of TiB2 is remarkably diboride, can endure temperatures of 1500 to 1700 K without
low, being only one-fifth of that for metallic titanium. The extensive attack. In this case, a surface layer of the parent
band gap of the three semiconductors mentioned are 0.20, 1.6, oxides is formed at a relatively low temperature, which
and 1.36 eV, respectively (see Semiconductors). prevents further oxidation up to temperatures where the
Superconductors of the RET4 B4 system are interesting for volatility of boron oxide becomes appreciable. In other cases
the study of the interplay between superconducting and mag- the oxidation is retarded by the formation of some other type
of protective layer, for instance, a chromium borate. This
netic order (see Superconductivity). The RET4 B4 compounds
behavior is favorable and in contrast to that of the refractory
represent a great variety of correlated electron phenomena,
carbides and nitrides, which form gaseous products (carbon
consisting of ferromagnetism, antiferromagnetism, supercon-
oxides and nitrogen) in air at high temperatures. Boron carbide
ductivity, valence fluctuation, or Kondo lattice anomalies, and
is less resistant to oxidation than the metallic borides.
effects which arise from their interplay in the structure.47
Borides, especially those of group IV transition metals,
Another very interesting group of superconducting, boron-
exhibit a high resistance to attack by molten metals and
containing materials are borocarbides of the composition nonbasic slags and salts. These properties make them
RET2 B2 C (T = Ni, Pd, Pt). The compounds of this group attractive as materials for vaporization boats (TiB2 , hex.
show a relatively high Tc if the rare-earth ions are large, that BN), for crucibles and containers for liquid metals, for
is, (La, Pr).43 It was discovered recently (2001), that MgB2 example, Al, and for protective tubes of thermocouples.50
(known since the 1950s) is a superconductor at as high a tem- Composites of TiB2 and BN are frequently also used as
perature as 39 K. This surprising discovery initiated a large boats for vacuum metallizing of capacitor foils and car
number of investigations of iso-structural binary and ternary mirrors. Titanium diboride is also utilized for collector
compounds to reveal its basic properties and to search for bars in the aluminum reduction process owing to its low
other related compounds with even higher Tc :s.48 resistivity and great inertness toward liquid aluminum.50 A
The excellent permanent magnetic properties of materials major part of the boride production is used for chemical
based on Nd2 Fe14 B were discovered in 1983.49 Very soon and metallurgical applications. Calcium hexaboride is, for
afterwards strong, small permanent magnets were available instance, used as a deoxidation agent in copper production,
commercially with a Curie temperature of 850 K and a very which results in higher conductivity than conventionally
high energy product (BH)max . This quantity for Nd2 Fe14 B is phosphorus-deoxidized copper owing to the low solubility of
Melting
temperature Microhardness Hf Resistivity Tc
Phase (K) (GPa) (kJmole1 ) (ohmm108 ) (K)
MgB2 1100a 11 92 16 39
TiB2 3500 33 280 7 15
ZrB2 3450 29.4 305 7 10 5.5
CrB 2400 12 13 45
CrB2 2500 21 130 21 56
Fe2 B 1660a 13.5 38
FeB 1925 19 38 80
CaB6 2770 27 120 >200
LaB6 3000 27.7 400 7 15 0.12
CeB6 2825 30 >350 29
-AlB12 1725a 37 105
YB66 2300 38 360106
h-BN 2.3 255 Insulator
c-BN 2700 60 70 Insulator
B4 C 2725 45 242 105 107
a
Decomposes.
BORIDES: SOLID-STATE CHEMISTRY 11
boron in copper. Large amounts of AlTiB alloys, containing the properties by doping. The boron-rich borides, which dis-
TiB2 , are used as grain refiners in the aluminum industry. play charge carriers with extremely low mobility, are thus
The most attractive properties of boron-containing intermediate between crystalline and noncrystalline solids as
materials, in particular diborides and boron carbide, are regards certain properties, which probably can be ascribed
the high melting point, the high hardness (see Table 4), to their complex and defect-rich structures. Optical stud-
the excellent wear resistance, and the favorable chemical ies of boron and boron-rich borides have led to invaluable
inertness. However, they are brittle, so special precautions information on the electronic and vibrational structure of the
must be taken in their exploitation. They can be used as compounds.56
coatings, either as thick films obtained by packboronizing Recently, semiconducting refractory boron compounds
of structural parts in B4 C powder at high temperature, have been suggested for high-temperature thermoelectric
or as thin films obtained by chemical vapor deposition or energy conversion.57 For such an application, the corre-
physical vapor deposition (see Chemical Vapor Deposition) sponding figure of merit requires high values of the Seebeck
techniques. Hexaboride coatings are even attractive to be coefficient and the electric conductivity, and a low value of the
used as decorative coatings on consumer products.51 In these heat conductivity of the material even at high temperatures.
cases advantage is derived from the combination of a ductile The thermoelectric properties, high melting points, and chem-
core and a wear-resistant adhesive coating. Another solution ical inertness of boron carbide and related boron compounds
to the brittleness problem is to produce a composite with a make them of special interest in such a context. Another recent
ductile binder, that is, a boride cermet or a cemented boride, application, where the electrical properties are decisive, is the
in analogy to the cemented carbides. This has led to the use of LaB6 and CeB6 as thermionic emitter materials in appli-
presently active research interest in cemented borides utilizing cations where very high brightness is required.58 The materials
TiB2 as hard substance and iron, iron-based or nickel-based mentioned are used in electron microscopes and electron beam
binders. The results indicate that dense sintered parts with lithography systems. The borides are preferred to the conven-
good chemical stability and attractive mechanical properties tional tungsten emitters owing to their higher brightness and
can be obtained.52 Promising results have also been obtained longer service life, although they are more expensive.
from studies of the cermet Mo2 FeB2 with an iron-based binder The structurally complex semiconducting boride, YB66 ,
phase.53 with a cubic unit cell axis of 23.44 A, has been found to
The utilization of the outstanding mechanical and wear be an excellent monochromating material for synchrotron
properties of cubic BN and related superhard materials has radiation.36 In this application the attractive properties are
high vacuum and thermal stability, good mechanical strength,
been demonstrated, although further process improvements
and radiation-damage resistance and low thermal expansion
are necessary before a more general use can be expected.
coefficient. It is also essential that large, high-quality
Superhard cubic BN exhibits superb inertness to hot steel
single crystals can be grown, which has been demonstrated
surfaces under conditions in which diamond would be severely
successfully.
attacked. Other tetrahedral structures, for instance, BCN and
B2 O, are anticipated to display similar attractive properties.
The high-pressure phase B2 O is a semiconductor with a band
gap of 0.25 eV and a hardness between that of boron carbide
and diamond. 6 RELATED ARTICLES
Boron carbide is a relatively inexpensive hard material,
which is used for its mechanical properties of strength and Boron: Inorganic Chemistry; Carbides: Transition Metal
extreme hardness in armor-plates for body protection, in Solid-state Chemistry; Nitrides: Transition Metal Solid-state
sandblast nozzles, and as an abrasive for grinding and cutoff Chemistry.
wheels.54 In nuclear plants, boron carbide is used as the
neutron absorbing material of the control rods.
Intense research has in recent years been devoted to non-
crystalline materials. It was discovered also that the majority 7 REFERENCES
of semiconducting boron-rich borides display several proper-
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12 BORIDES: SOLID-STATE CHEMISTRY
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York, 1991, p. 165.
Boron Hydrides H
H
H
H
H
H
C C B B
H H
H
Narayan S. Hosmane1 & John A. Maguire2 H H H
1 C2H6 B2H6
Northern Illinois University, Dekalb, IL, USA
2
Southern Methodist University, Dallas, TX, USA 14 valence electrons 12 valence electrons
14 valence orbitals 14 valence orbitals
1 Introduction 1 on the rectangular open face. Note that the lines drawn in the
2 Nomenclature 3 structures show connectivity and do not necessarily indicate
3 Syntheses 3 2c 2e bonds.
4 Reactions 4 A useful molecular orbital description can be developed
5 Related Articles 4 by considering each boron atom to be sp hybridized with
6 References 5 one sp hybrid pointed toward the center of the cage (radially
oriented) and the other pointed directly toward its terminal
hydrogen, with the two p orbitals oriented tangentially to
the cage.2,3 The outwardly oriented orbital could overlap
with a hydrogen s orbital to form a 2c 2e bond, using one
electron from the boron and one from the hydrogen. The
1 INTRODUCTION radially directed and the two tangentially directed orbitals
on each boron can be combined to give the cage molecular
Boranes are mixed hydrides of boron and hydrogen.1 The orbitals. These molecular orbitals (MO) will be filled by the
unusual properties of these compounds arise from the fact that two electrons left on each boron, those from charges, plus
in forming compounds, boron can furnish four orbitals (s, px , one additional electron from each bridging hydrogen. For
py , pz ) but only three electrons for bonding. Since the num- example [B6 H6 ]2 , which has a closed (closo-) octahedral
ber of orbitals exceeds the number of electrons, the boranes structure, will have 18 boron based orbitals (AO) for cage
are sometimes referred to as electron-deficient compounds. bonding and 14 (2 6 + 2) cage electrons. The 18 AOs will
The consequence of this imbalance can be seen in comparing yield 18 MOs, 7 of which are bonding and 11 antibonding.
the two simple hydrides of carbon and boron, that is, ethane The 14-cage electrons are enough to fill the bonding MOs
(C2 H6 ) and diborane (B2 H6 ), using valence bond formalism. for a stable structure. In general, a closed polyhedral cage,
Their Lewis diagrams are shown in Figure 1. The structure composed of fused deltahedra, with n vertices will have 3n
of ethane can be understood in terms of seven two-electron- AOs for cage bonding that give rise to n + 1 bonding MOs
two-center bonds (2e 2c) formed between adjacent atoms. and 2n 1 antibonding MOs.24 Therefore, such structures
However, such a description is not possible for diborane, should be stabilized by 2n + 2 cage electrons. Inspection of
since there are not enough electrons. The bonding description Figure 2 shows this to be the case. Analysis also shows that
that is depicted in Figure 1 shows the molecule as consisting the addition of two electrons to closo-[B6 H6 ]2 causes the
of two BH2 units, in which the two hydrogens (the termi- cage to open, giving the pentagonal pyramidal nido-[B6 H6 ]4
nal hydrogens) are attached by 2e 2c bonds, with the BH2 cage (which can pick up four bridge hydrogens). Considering
units joined by two BHB 3c 2e bridged bonds. Although only the fate of the cages, the [B6 H6 ]4 has 16 cage electrons
the bonding can better be understood using molecular orbital that fill 8 (n + 2) bonding MOs. Note that one could obtain
theory, the above description does introduce some common this pentagonal pyramidal cage by removing a single vertex
descriptive terms, that is, multicentered bonds and bridged and from a seven vertex closo-cage (the closo-[B7 H7 ]2 shown
terminal hydrogens. Figure 2 shows the structures of diborane in Figure 2). This brings up a very important relationship:
and some higher boranes. removal of one or more vertices from a closo-cage does not
The structures are drawn as polyhedra composed of fused change the number of bonding MOs.4 This forms the basis of
triangular faces (deltahedra), in which boron atoms, bonded the polyhedral electron-counting rules (Wades rules). Table 1
to at least one terminal hydrogen, occupy the vertices; bridge summarizes these rules and Figure 3 shows the progression of
hydrogens are shown for the nido-complexes.1 For example, several important structural types from closo (closed) to nido
B5 H9 (pentaborane(9)) has five boron atoms at the vertices (nest-like) to arachno (spiderweb-type).5 Further removal
of a square pyramidal cage, each one of which is bonded would lead to more open structures (hypo, fisco, reticulo).
to an exo-polyhedral hydrogen (a terminal hydrogen). In Other hybridization schemes could be used; as long as
addition, there are four hydrogens bridging adjacent borons they result in one radially directed and two tangential orbitals
2 BORON HYDRIDES
= Boron = Hydrogen
closo nido arachno that forms a single bond (halogen, CH3 , NH2 , etc.) without
changing any structural particulars. Also, the replacement
of a BH vertex by any group that can furnish a radially
directed and two tangentially directed orbitals for cage bonding
(i.e. is isolobal with BH), and contribute two electrons,
should not substantially change cage geometry. The same
would be true when a BH is replaced by a three-orbital,
i ii iii three electron group. This leads to a series of mixed atom
cages, called heteroboranes.2 When the hetero-atom is a
metal, the term metallaborane is used. One of the most
important such heteroboranes are those in which two CH
groups replace BH vertices in a closo-[Bn Hn ]2 cage to
give a neutral closo-[C2 Bn2 Hn ] cage. Since the neutral
dicarbaboranes (carboranes) are more stable and easier to
iv v vi
work with than are their borane analogues, more studies have
been conducted on carboranes than on the parent boranes.6,7
In general, all the main group elements, with the appropriate
substituents, can be thought of as being isolobal with boron.
Therefore, the electron-counting rules can be applied to other
main group elements by using a formalism in which the
particular cage element, X, brings to cage bonding its valence
electrons (v), plus those from other ligands attached to it
(x), less the two associated with exo-polyhedral interactions
vii viii ix or (v + x 2) electrons, as listed in Table 2. A number
of heteroboranes, and carboranes incorporating other main
group elements have been characterized.7 Electron-counting
Figure 3 Cage structures
rules can be extended to transition metal substitution by
assuming that the metal group will have 12 of its v + x
for cage bonding, they would give the same result. The electrons not involved in cage bonding; Table 3 gives the
utility of these rules can be extended by noting that the electron contributions for the groups 6 through 10 metals.8,9
terminal hydrogens could be replaced by any atom or group Using these numbers and the rules from Table 1, the
BORON HYDRIDES 3
Structural type
Table 2 Skeletal electron contributions of main group cluster When possible, preference is given to the nonboron atoms by
units (v + x 2)a assigning them the lowest numbers. When there is no unique
apical atom, the atom with the lowest coordination number
Cluster unit
MR2 is assigned the position 1. This numbering system, along
Group M MR or ML with the standard replacement nomenclature rules taken from
number Element (x = 0) (x = 1) (x = 2) organic chemistry, are used in naming the heteroboranes. This
1 Li, Na 0 1
can lead to names that are as impressive as the formulas.
2 Be, Mg, Zn, Cd 0 1 2 For example, in Figure 4, closo-2,3-(CH3 )-1,2,3-SnC2 B9 H9 is
13 B, Al, Ga, In, Tl 1 2 3 2,3-dimethyl-1-stanna-2,3-dicarba-closo-dodecaborane(12),
14 C, Si, Ge, Sn, Pb 2 3 4 closo-1-(CH3 )-1,2,3-GaC2 B4 H6 is 1-methyl-1-galla-2,3-
15 N, P, As, Sb, Bi 3 4 dicarba-closo-heptaborane(7), while arachno-[B9 H13 ]2 is
16 O, S, Se, Te 4 5
tridecahydro-arachno-nonaborate(2). More times than not,
a
v = No. valence electrons on M; x = No. electrons from ligands formal names are avoided in preference to formulas.
on M; R = one-electron ligand or H; L = two-electron ligand.
H H
S H H
Co
B N
H H
H
H B B
H H
H
Sn H3C
H 2
H3C C Ga H
H (OC)3 Fe
H3C H
C
= CH = BH
2KBH4 (s) + 2H3 PO4 (l) B2 H6 (g) + 2NaH2 PO4 (s) + 2H2 (g) These boranes react with acetylenes (RCCR ) to give,
(3) respectively, nido-2-R-3-R -2,3-C2 B4 H6 and closo-1-R-2-R -
1,2-C2 B10 H10 .18 The closo-C2 B10 carboranes can be degraded
2M[BH4 ] + 2BX3 B2 H6 + 2M[HBX3 ] (4)
to give nido-7-R-8-R -7,8-C2 B9 H11 cages or reduced directly
to give the corresponding nido-7-R-8-R -7,8-C2 B10 H12 . These
anhydrous acid (equation 3).13 Hydride abstraction from
nido-carboranes have two bridged hydrogens that can be
[BH4 ] by BX3 (equation (4)) has also been described.
removed to give the more reactive dianions that undergo met-
It should be stressed that diborane is an extremely
allation reactions and are used as ligands that closely resemble
toxic, flammable, and explosively reactive gas that should
cyclopentadienide ([C5 H5 ] ) in their bonding interactions. A
be handled with extreme care. The controlled pyrolysis
number of main group,7,17 transition metal6 and rare earth19
of B2 H6 yields higher boranes plus H2 , culminating in
decaborane(14) (B10 H14 ), which is quite stable. Hydride ion metallacarboranes of these and other carboranes have been
abstraction reactions of lower molecular mass hydroborates reported and studied.
by BX3 has also produced a number of neutral boranes in good In the last 50 years, there has been a wealth of fascinating
yields.14 Other methods that target specific boranes, such as chemistry published on the boranes and heteroboranes.1 Their
B5 H9 and B10 H14 , have also been described.15 unique structures have forced us to rethink our ideas on
bonding and they have proven to be invaluable reagents in
other areas of chemistry.20
4 REACTIONS
94%
2 of detail, most of the subjects included in this article.1321
1.47 MeV 0.84 MeV 0.48 MeV
Each section contains additional, more specific references.
10B
5
+ 1nthermal [115 B]
6%
7Li
2He + 3
4
boron filaments. There are numerous small to moderate example, high electrical and thermal conductivity. Most of
volume uses for elemental boron. Perhaps the most prominent them have high melting points, high hardnesses, and good
is the use of boron filaments deposited on tungsten wire as resistance to chemical attacks. The boron-rich metal borides,
reinforcements in plastics, such as epoxy resins, and metal having compositions ranging from MB6 to MB60 or greater,
composites, such as aluminum and titanium. These boron are among the hardest known substances.
fiber-reinforced composites have an exceptional compressive Most borides are inert toward nonoxidizing acids, although
strength and are used in aerospace applications and in sporting Be2 B and MgB2 react with aqueous acids to form boron
goods, including golf club shafts, tennis racket frames, and hydrides. Oxidizing acids such as nitric or hot sulfuric dissolve
fishing rods. Elemental boron has also been used as a fuse to most borides. Hot alkaline salt melts and fused alkali peroxides
initiate release of nitrogen gas in automobile air bags by its also dissolve borides to form the more stable borates. Borides
rapid reaction with sodium azide. are generally resistant to oxidation in dry air due to the
Many forms of elemental boron have been reported in the formation of a protective oxide layer. Many borides do not
literature. The presence of trace impurities can have major oxidize in air below 1000 1400 C.
effects on the structure and properties of boron, in some cases More than one boride phase can be formed with most
leading to false identification of unique forms. Crystalline metals, and in many cases a continuous series of solid
boron exists in at least three allotropic forms depending solutions may be formed. Several methods have been used
on the preparative method used. The structures of the - for the relatively large-scale preparation of metal borides.
rhombohedral, -rhombohedral, and -tetragonal allotropes One that is commonly used is carbon reduction of boric
have been defined by X-ray diffraction studies and shown oxide and the appropriate metal oxide at temperatures
to each incorporate B12 icosahedra in their structures. Similar up to 2000 C. Fused salt electrolysis of borax or boric
icosahedral structures exist in boron carbide, boron phosphide, oxide and a metal oxide at 700 1000 C have also been
B12 P2 , and boron arsenide, B12 As2 , discussed below. Details used. Small-scale methods available include direct reaction
of the structures of these allotropes can be found in Borides: of the elements at temperatures above 1000 C and the
Solid-state Chemistry. The -tetragonal allotrope, originally reaction of elemental boron with metal oxides at temperatures
thought to consist of B12 icosahedra linked by B2 units, now approaching 2000 C. One commercial use of borides is
appears to be an impure boron phase with B12 icosahedra in titanium boride aluminum nitride crucibles or boats
linked by C2 or N2 units. for evaporation of aluminum by resistance heating in the
Amorphous boron (>90%) melts at 2300 C, sublimes at aluminizing process, and for rare earth hexaborides as
approximately 2550 C, and has a density of 2.35 g mL1 . electronic cathodes. Borides have also been used in sliding
Crystalline -rhombohedral boron melts at temperatures in electrical contacts and as cathodes in Hall cells for aluminum
the range 2180 2190 C, sublimes at 3650 3660 C, and processing.
has a density of 2.45 g mL1 . The crystalline forms are hard The discovery that magnesium diboride, MgB2 , is a
refractory materials with Mohs hardnesses in the range of superconductor with a transition temperature of 39 K was
9 11, compared to 15 for diamond. first announced in 2001.26 Although 39 K does not qualify
In general, both crystalline and amorphous boron are magnesium diboride for the status of a high-temperature
relatively inert materials with the amorphous form tending superconductor, it is a record high transition temperature
to react more readily with chemical reagents. Finely divided for a relatively simple and inexpensive material. Magnesium
micron-sized amorphous boron can react violently with diboride was well known for decades prior to this discovery,
hydrogen, oxygen, and chlorine at elevated temperatures and but prevailing theories of superconductivity did not predict this
with water above 100 C. Crystalline boron can be dissolved high transition temperature. Thus, this discovery resulted in a
in a hot 2:1 mixture of sulfuric and nitric acids, but is nearly resurgence of interest in superconductivity and the possibility
inert toward oxygen, water, nitric acid, and sodium hydroxide. of developing a new class of low-cost high-performance
superconductor materials.27
Magnesium diboride is a metallic compound having a
2.3 Metal Borides structure in which boron atoms form hexagonal layers with
magnesium atoms located between the layers above and
A large number of binary metal borides have been prepared below the centers of the boron hexagons. The unusual
and characterized. Their stoichiometries vary from M5 B to properties of this material are thought to result from strong
MB100 , but the most common are M2 B, MB, MB2 , MB4 , interactions between lattice vibrations (phonons) and the
MB6 , and MB12 . The structures of metal borides vary from electronic structure of the boron layers. It is proposed that the
isolated boron atoms in borides from M4 B to M2 B, to chains of anomalous superconducting properties of magnesium diboride
boron atoms in MB and M3B4 , to two-dimensional networks of can be explained by the presence of two, rather than the usual
boron atoms in MB2 and M2 B5 , to complex three-dimensional one, superconducting energy gaps in this material.28 These
arrays of boron atoms in MB4 , MB6 , and MB12 . In general, gaps correspond to transition temperatures of 15 K and 45 K,
metal borides exhibit characteristics of typical metals, for and combine to give an overall transition temperature of 39 K.
4 BORON: INORGANIC CHEMISTRY
The tertiary alloy of composition AlMgB14 , referred to as carbon, or B12 C3 , the structure is composed of B11 C icosahedra
BAM, has a hardness similar to industrial diamond. Since linked by CBC chains. With decreasing carbon content from
its discovery was reported in 1999, BAM has been the subject 20 to 13%, the CBC chains are progressively replaced by
of intense research interest.29 It is reported to be an excellent CBB chains, and below 13%, the B11 C icosahedra are
material for use in cutting tools. One unique property of this replaced by B12 icosahedra.
ultrahard substance is its ability to cut hot materials without The properties of boron carbide are similar to elemental
becoming hot itself. It is also less reactive with steel than boron. It has a theoretical density of 2.52 g mL1 and a
diamond is, and so can be used to cut both masonry and steel. melting point of approximately 2400 C. Boron carbide has a
Although still produced on a laboratory scale, current efforts high compressive strength, but its tensile strength is limited.
are focused on developing methods for its manufacture on Boron carbide is prepared commercially by the reduction of
industrial scale. This has required development of improved boric oxide with carbon in a hydrogen atmosphere in an
methods for the preparation of high-purity low-oxygen content electric furnace at 1400 2300 C (equation 1). In a related
elemental boron, since oxygen impurity lowers the hardness reaction, magnesium is added to boric oxide in the presence of
of BAM by forming spinel, Al2 MgO4 . The use of BAM may carbon black at 1400 1800 C (equation 2), and magnesium-
eventually reduce energy consumption and other wear-related containing by-products are removed by acid treatment.
costs in industrial cutting and grinding operations.30 Usually, boron carbide is converted to a granular form that can
Another important application of metal borides is in be molded or bonded into useful shapes. In order to achieve
permanent magnets. Metal boron alloys such as neodymium high strengths and high densities, boron carbide is hot pressed
iron boron, having a base composition of Nd2 Fe14 B, exhibit at 1800 2400 C in graphite molds. Although it is brittle and
the highest energy product of any readily available magnetic sensitive to thermal shock, the exceptional hardness of boron
material. Produced commercially since the early 1980s, rare carbide, with a Mohs hardness of approximately 10 compared
earth magnets are used extensively in the manufacture of hard to 15 for diamond, has resulted in moderate commercial usage
disc drives, high-performance electric motors, speakers, and in its hot-pressed form in ceramic armor plates, sandblasting
instruments. These magnets are typically manufactured using nozzles, wear parts, and in dressing grinding wheels. Because
a metallurgical process in which a powder of the appropriate of its radiation stability, chemical inertness, and the ability of
alloy composition is first produced and then sintered into the boron to capture neutrons, boron carbide has also found use
desired shape for a given application.31 A coating of protective in radiation shielding and control devices in nuclear reactors.
material, such as nickel, is often applied to Nd Fe B magnets
because they tend to be susceptible to oxidation. 2B2 O3 + 7C B4 C + 6CO (1)
2B2 O3 + 6Mg + C B4 C + 6MgO (2)
atmospheric pressure. Its theoretical density is 2.27 g mL1 . Another commercial form is known as pyrolytic boron
In contrast to graphite, hexagonal boron nitride is a good nitride, p-BN. This form is a variation of standard h-BN and is
electrical insulator. Cubic boron nitride has a theoretical manufactured by pyrolyzing boron trihalides in the presence of
density of 3.49 g mL1 , a structure resembling diamond, and ammonia at about 2000 C and allowing the pyrolysis products
a Mohs hardness near the maximum of 15 for diamond. to deposit on a graphite substrate. This process results in
Cubic boron nitride is widely regarded as the second hardest boron nitride having a high degree of crystal orientation, with
substance known after diamond. hexagonal layers running parallel to the substrate surface. This
Hexagonal boron nitride can be prepared by a variety gives anisotropic characteristics valuable in the fabrication of
of reactions starting with boric oxide, boric acid, or borate articles, such as high-temperature crucibles. Pyrolytic boron
salts. These include heating boric oxide or boric acid with nitride has exceptional thermal properties, high tensile strength
ammonia, and heating boric oxide, boric acid, or borate that increases with temperature, and the highest dielectric
salts with ammonium chloride, alkali metal cyanides, or properties of any readily available material. It is also extremely
calcium cyanamide. High-purity hexagonal boron nitride can resistant to attack by most chemical reagents even at high
be prepared by reaction of ammonia with boron trichloride or temperatures.
boron trifluoride. The rhombohedral form of boron nitride is Crystalline cubic boron nitride is mainly used as an
prepared by rapid heating of a mixture of sodium borohydride extremely hard abrasive, similar to how industrial diamond
and ammonium chloride to 750 1000 C in the presence of is used. As 1 500 m particles, it is sold as an abrasive
added sodium chloride. Both hexagonal and rhombohedral material with trade names including Borazon and Amborite.
boron nitride can be converted to the cubic zinc blende This material is used in cutting tools and as grit for grinding
form by heating at 1400 1700 C and 4 6 GPa pressure. and polishing wheels. Cubic boron nitride is bonded into
This conversion is accelerated by the presence of additives cutting tools used to shape hard ferrous- and nickel-based
including lithium and alkaline earth nitrides and amides. The alloys, which tend to react with diamond cutting tools, and
wurtzite form is obtained in the absence of additives at higher also to cut masonry and glass.
pressures. Subsequent to the much acclaimed discovery of carbon
The various forms of boron nitride are all relatively inert nanotubes, techniques were developed to prepare boron nitride
to chemical attack under normal conditions. For example, nanotubes.33 These bear a similar isostructural relationship to
hexagonal boron nitride does not react with oxygen, chlorine, carbon nanotubes as diamond and cubic boron nitride, and can
or steam up to 700 C. Reaction with steam begins at 900 C. be prepared as multiwall tubes.34 Boron nitride nanotubes have
Rapid reactions are observed with hot alkali or fused alkali been prepared by electric arc-discharge in the gas phase and by
carbonate, but reactions are slow with most acids and alcohols, depositing boron and nitrogen ions on a hot, electrically biased
and boron nitride is not wetted by most molten metals and tungsten surface. Boron nitride nanotubes have some potential
glasses. The cubic forms have similar reactivity but rates are advantages over carbon nanotubes in being more resistant to
slower because of their dense structures. oxidation and thus suited for high-temperature applications.
Both hexagonal and cubic boron nitride are important In addition, BN nanotubes are expected to be semiconducting
commercial products, and consumption of both forms has with conductivities less dependent on the specific nanotube
gradually increased in recent years. Hexagonal boron nitride geometry.
is used as a lubricant and release agent in engineering
polymer and molten metal extruding and forming operations.
Hexagonal boron nitride is a good electrical insulator and a 2.6 Boron Phosphides
thermal conductor, a combination of properties that leads to
applications in the electronics industry. In this application, Two boron phosphides have been isolated, BP and B12 P2 .
h-BN is blended into elastomeric or thermoplastic parts used Heating elemental boron and red phosphorus at 900 1100 C
to transfer heat away from electronic components while yields BP as refractory brown crystals having a cubic zinc
maintaining electrical insulation. Hexagonal boron nitride blende structure similar to cubic boron nitride. This material
powder is often hot-pressed at temperatures up to 2000 C can also be prepared by a number of other methods including
and pressures up to 14 Mpa to form articles of various the pyrolysis of Cl3 PBCl3 , reaction of boron or boron
shapes, such as high-temperature vessels. Its low coefficient trichloride with zinc phosphide or phosphine, and hydrogen
of thermal expansion, excellent thermal shock resistance, and reduction of Cl3 PBC13 .
resistance to chemical attack makes such vessels useful for Cubic boron phosphide is a III V semiconductor with
many high-temperature processes. Hexagonal boron nitride is a large band gap. It is stable to 2500 C at high pressure
often combined with other nonoxide ceramic materials and but decomposes at 1100 C under vacuum with elimination of
intermetallic composites to improve their physical properties. volatile white phosphorus, and formation of gray B12 P2 , which
Hexagonal boron nitride is sold as powders and hot-pressed can be recrystallized from molten iron or aluminum to give
articles, as well as paste and liquid dispersions in water or black crystals. X-ray studies indicate that this material contains
organic solvents for use as coatings and aerosol sprays. B12 icosahedra linked by P2 moieties. The related boron
6 BORON: INORGANIC CHEMISTRY
arsenide, B12 As2 , has a similar structure with the icosahedra and above 800 C, the strong boroxin line in the Raman
joined by As2 moieties. spectrum disappears. Above 800 C, the melt apparently
consists of strongly associated discrete small molecules. The
large discrepancy between spectroscopic observations and
calculations may be related to the inability of computations
3 BORIC OXIDES, BORIC ACIDS, AND METAL to accurately simulate realistic cooling rates. Structures of
BORATES the crystalline forms of B2 O3 have been determined. The
B2 O3 -I crystalline phase is hexagonal with trigonal boron-
geometry. The crystal lattice of monoclinic B2 O3 -II consists
3.1 Introduction of a compact network of BO4 tetrahedra with the four apical
oxygens that are shared by two or three boron atoms. The
Boric oxides, boric acids, and metal borates are of primary Lewis acid character usually associated with trigonal BO3
importance in any discussion of boron chemistry since these groups is absent in this crystalline form, and reactions with
include essentially all boron minerals and the vast majority of water and fluoride ion, as examples, are sluggish. Reaction of
boron compounds produced and used worldwide on a weight vitreous boric oxide with water is exothermic and gives boric
basis. Reviews of this chemistry and the commercial aspects acid (equation 3). Vitreous boric oxide is mildly hygroscopic
of this general subject are available.2,18 at room temperature, and commercial samples usually contain
approximately 1% water as a surface layer of boric acid.
3.2 Boric Oxides Molten boric oxide reacts readily with water above 1000 C
to form metaboric acid vapor (equation 4).
Reviews of boron oxide chemistry are available.13,35 The
fundamental material B2 O3 is referred to in the literature B2 O3 + 3H2 O 2B(OH)3 (3)
as boric oxide, boron trioxide, and diboron trioxide. In the B2 O3 (molten) + H2 O(g) 2HBO2 (g) (4)
commercial context it is called boric oxide, anhydrous boric
acid, boric anhydride, and boric acid anhydride. This material, Values for the physical properties of boric oxide are
the only significant commercial form of boric oxide, is usually somewhat confused in the literature due to the tendency of
isolated as a vitreous solid at room temperature. It is prepared this substance to react readily with water. Many physical
in large quantities by fusing refined boric acid in a furnace. properties of boric oxide are sensitive to water content,
The resulting molten glass is drawn out of the furnace, cooled and the water content of samples used for measurements
on chill rolls, crushed, and screened. Two crystalline forms of was not always carefully controlled. For example, at 0.28%
B2 O3 have been prepared in laboratory quantities. The form, water, the density of vitreous boric oxide is 1.853 g mL1
or B2 O3 -I, is prepared as hexagonal crystals by seeding with and the softening point 240 275 C. Reducing the water
this form or with boron phosphate at 250 C. The more exotic concentration to 20 g g1 reduced the density to 1.829 g mL1
form has only been obtained by heating vitreous boric oxide and raised the softening point to 300 325 C.37 Other
at 400 C and 22 000 atmospheres. Some physical properties properties, such as thermal expansion, viscosity, and refractive
of the vitreous and crystalline forms are shown in Table 1. index, are also significantly affected by moisture content.
Structural features of vitreous and molten boric oxide have Water concentrations can be reduced to as low as 10 g g1
been subject to debate. It appears that only trigonal boron is by prolonged heating in vacuum.
present in the solid glass, in a branched network containing In addition to its reactivity toward water, the Lewis acidity
(BO)3 boroxin rings. The percentage of boron in B2 O3 of boric oxide leads to coordination with even relatively weak
glass participating in boroxin rings has been controversial. bases to form tetrahedral boron species. Molten boric oxide
Spectroscopic data indicate that 60 70 mol percent of boron dissolves most metal oxides at high temperatures (>1000 C),
in this material is present in boroxin ring structures; however and is therefore corrosive to metals in the presence of oxygen.
theoretical calculations have predicted only 15 20%.36 Boric oxide reacts readily with alcohols to form boric acid
As the glass melts, boroxin ring structures break down, esters and boroxins, and with P2 O5 to give boron phosphate.
Because of its fluxing action, boric oxide is used as a solvent
Table 1 Some physical properties of boric oxides for metal reductions, for growing crystals at high temperatures,
and in the preparation of metal salts such as lead titanate and
Crystalline forms calcium zirconate from the oxides. The general fluxing action
Property Vitreous form B2 O3 -I B2 O3 -II of boric oxide is important in preparing many types of glasses,
glazes, frits, ceramic coatings, and porcelain enamels, and this
Mp ( C) Softens 300 325 455 475 510 property is also utilized in soldering and welding fluxes. Boric
Bp ( C) 2316 (extrap.)
oxide is a chemical intermediate in the production of a variety
Density (g mL1 ) 1.84 2.46 2.95
B-O geometry trigonal trigonal tetrahedral of other boron compounds, including esters, carbides, nitrides,
and metal borides.
BORON: INORGANIC CHEMISTRY 7
3.3 Boron Suboxides The formula B(OH)3 denotes the correct structure (1) and is
preferred to H3 BO3 , which gives the misleading impression
Boron suboxides have boron:oxygen mole ratios equal to that boric acid is a tribasic Brnsted acid such as H3 PO4 . Boric
or greater than one. These compounds range from molecular acid occurs as the relatively rare mineral sassolite that at one
species to refractory solid-state materials. Monomeric vapor- time was extracted commercially from hot springs in Italy.
phase BO and B2 O2 have been studied by spectroscopic Metaboric acid, HBO2 or B2 O3 H2 O, has been isolated in
techniques. In addition to these rather unstable high- three crystalline modifications (see Section 3.4.3), including
temperature species, several forms of solid noncrystalline the boroxin or orthorhombic form (2). Summaries of boric
boron suboxides have been reported. A water-soluble low- acid chemistry are available.13,39,40
temperature form is obtained by the vacuum dehydration of
tetrahydroxydiborane at 220 C (equation 5). At 500 C, this
form converts to a light brown modification that has also been OH
obtained by reactions of boric oxide with elemental boron, OH B
boron carbide, or carbon at high temperatures (>1250 C). B
O O
HO OH B B
HO O OH
nB2 (OH)4 (BO)2n + 2nH2 O (5)
(1) (2)
cotton batting for mattresses and furniture. Boric acid is also Table 3 Solubility of boric acid
used in nuclear reactors because of the high neutron-absorbing
cross section of the 10 B isotope. It is also used as an additive Temp. ( C) B(OH)3 dissolved (wt%)
in the air oxidation of hydrocarbons, and related reactions, 0 2.52
where its presence hinders unwanted oxidation side reactions. 20 4.72
Although the melting point of boric acid is given as 40 8.08
50 10.27
170.9 C, some water loss occurs at temperatures as low
60 12.97
as 100 C when boric acid is heated slowly. Below 160 C, the 80 19.10
vapor phase includes water and gaseous boric acid. Boric acid 100 27.53
is volatile in steam, and loss of boric acid from boiling aqueous
solutions can be a problem in some industrial operations. At
higher temperatures (600 1000 C), gaseous metaboric acid aqueous chemistry of boric acid. The calculated equilibrium
is the principal compound formed by equilibration of water constant for the reaction shown in equation (6) is 5.80 1010
vapor and molten boric oxide.42 at 25 C.
Equilibrium
Table 2 Some properties of boric acids Acid constant (mol L1 )
Property H3 BO3 HBO2 -III HBO2 -II HBO2 -I Phosphoric 7.5 103
Acetic 1.75 105
Mp ( C) 170.9 176 200.9 236 Boric 5.80 1010
Density (g mL1 ) 1.517 1.784 2.045 2.49 Silicic 2 1010
BORON: INORGANIC CHEMISTRY 9
3.5
8.2
3.0
8.0 8.4
7.8
2.5 9.8
8.8
7.6 8.6 9.6 10.0
9.0
B2O3, wt %
10.2
1.5
10.4
1.0
0.5
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Na2O:B2O3, mol ratio
the solution pH becomes sensitive to concentration change, The addition of metal salts, particularly alkaline earth
as shown in Figure 1.43 This anomalous behavior results from cations and/or halides, can result in significant shifts in
the formation of the polyborate anions (36), which dissociate the monoborate-polyborate equilibria. Equilibrium constants
have been calculated for the equilibria between B(OH)3
and B(OH)4 and several polyborates: the pentaborate
HO O OH HO O OH monoanion (3), the triborate monoanion (4), the tetraborate
B B B B
dianion (5), and triborate dianion (6).44 Figure 2 illustrates
O O O O
B B the relative populations of borate species as a function of
O O HO OH pH for a B2 O3 concentration of 13.93 g L1 . The formation
B B of polyanions is particularly significant in the intermediate
HO O OH
pH range. These polyborate anions form successively in the
(3) (4)
order (3) to (6) with increasing pH and have been identified in
solution by their colligative properties and by Raman and 11 B
O NMR spectroscopy. These anions are also found in crystalline,
HO HO O OH
B O B B synthetic, and minerals borates. Alkali metal borate glasses
O HO OH probably contain similar structures.45
B B OH O O
B O O In addition to pH effects resulting from formation of
HO B
OH
OH polyanions in solution, significant enhancements in the
(5) (6) solubilities of boric acid and alkali metal borates are also
observed at certain mole ratios. For example, soluble borate
salts can be dissolved in saturated boric acid solutions
into the monomeric species B(OH)3 and B(OH)4 when the to produce solutions having significantly higher B2 O3
solutions are diluted. Below pH 9, the pH increases on dilution. concentrations. The formation of polyborate anions decreases
Above 9, the pH decreases with dilution. This is probably due the concentrations of B(OH)3 and B(OH)4 in equilibrium
to shifts in the equilibria between monomeric and polymeric with undissolved borate salts, thereby permitting more borate
species and their relative acidities. At a sodium:boron molar salts to dissolve. In the case of alkali metal borates, maximum
ratio of 0.41, the pH of 8.91 is independent of concentration. solubility is achieved at a metal:boron ratio of approximately
This ratio and the pH attained have been referred to as the 1:4. This provides the basis for the commercial product
isohydric point. The isohydric point for potassium solutions Na2 B8 O13 4H2 O (see Section 4.4), which dissolves readily
is slightly different from sodium solutions: pH 9.0 at a in water with little temperature change to form concentrated
potassium:boron ratio of 0.405. borate solutions.
10 BORON: INORGANIC CHEMISTRY
1.00
0.60
B(OH)3 B(OH)4
B3O3(OH)4
0.40
B3O3(OH)52
B5O6(OH)4
0.20
B4O5(OH)42
0
4 6 8 10 12 14
pH
It is important to note that the presence of polyborate high temperatures, often crystallizing from molten inorganic
anions, as shown in Figure 2, is only significant in relatively systems. It is unusual to obtain anhydrous borates from
concentrated solutions. This is relevant to the environmental aqueous solutions except occasionally under hydrothermal
and biological aspects of boron chemistry, since boron is conditions. In terms of tonnage, the vast majority of synthetic
present in both natural waters and biological systems at low industrial borates are hydrated, and most mineral borates also
concentrations. Under these conditions, only B(OH)3 and fall into this category. However, crystalline anhydrous borates
B(OH)4 are significant species; and at near neutral pH, the have received considerable attention in the scientific literature
concentration of the B(OH)4 anion is minor. Ocean waters because of their potential for use in smaller-scale advanced
contain an average boron concentration of about 4.6 g g g1 , technology applications, such as optoelectronic devices. The
which is almost entirely present in the form of naturally structural chemistry of anhydrous metal borates has been
occurring boric acid. Boron in plants and animals is also reviewed.46
present mainly as boric acid, even if the dietary source of Metal borates have been prepared in hydrated or anhydrous
boron is a borate salt. forms from most metals in the periodic table and have many
small to medium scale applications. The general method used
to prepare hydrated metal borates involves mixing an aqueous
solution of boric acid or an alkali metal borate with aqueous
4 METAL BORATES solutions or suspensions of metal oxides, halides, or sulfates.
The resulting precipitates of metal borates may be either
crystalline or amorphous solids of slight to moderate solubility.
4.1 Introduction Most metals can produce several different crystalline borates.
In the case of crystalline hydrated borates, the specific
Metal borates can be divided into two broad classes: crystalline form obtained generally depends on the relative
hydrated and anhydrous. So-called hydrated borates, which concentrations of starting materials and the temperature. Salts
have the general formula aMx ObB2 O3 CH2 O, contain B-OH of metals that produce highly insoluble hydroxides frequently
groups, sometimes interstitial OH , and may also contain produce complex hydroxide gels upon reaction with soluble
interstitial water. Anhydrous borates do not contain water, borate salts rather than metal borate compounds. These gels,
OH , or B-OH groups, and have the general formula which may contain significant amounts of adsorbed borate,
aMx ObB2 O3 . As crystalline compounds, hydrated borates have often been incorrectly described as true metal borate
typically crystallize from aqueous solutions under relatively compounds, particularly in the older literature. Anhydrous
mild conditions. Anhydrous borates nearly always form at metal borates are either prepared by dehydration of the
BORON: INORGANIC CHEMISTRY 11
appropriate hydrate at 300 1000 C, or by direct fusion of designation Na2 [B4 O5 (OH)4 ]8H2 O correctly identifies the
metal oxides with boric acid or boric oxide, with the crystalline tetraborate ion (5) in the crystalline compound and correctly
form produced governed by temperature and reactant ratios. defines the hydroxyl groups and waters of hydration.
Both hydrated and anhydrous metal borates have numerous
industrial uses. Some of the major uses of hydrated metal
borates are the manufacture of glasses, ceramics, and industrial 4.2 Borate Minerals
fluids, and as micronutrient fertilizers, fire retardants, and
Most boron-containing minerals are alkali metal and
biostats. Anhydrous borates find use as heterogeneous
alkaline earth borate salts. These compounds are the subject
catalysts, scintillation hosts, and in the fabrication of
of earlier reviews.2,15,47,48 More than 230 naturally occurring
optoelectronic devices. Anhydrous aluminum borates are used
borate minerals have been identified.2 The most abundant of
as additives in oxide ceramics to promote the formation of
these is the tourmaline group of aluminoborosilicate minerals,
desirable phases. Also, aluminum borate whiskers are used as
(Na,Ca)(Mg,Li,Al,Fe2+ )3 Al6 B3 Si6 (OH)4 , which may contain
reinforcing additives in composite materials. Specific uses of
roughly 10% boron by weight but have not been found
sodium, calcium, zinc, and barium borates are discussed in
in sufficient grades for economic mining. Concentrated,
sections below.
commercially exploitable borate deposits are found mainly
Two fundamental problems are encountered when dis-
in arid parts of the world. By far, the most extensive
cussing metal borates. One is nomenclature, and the other is
deposits have been located in Turkey and western United
the chemical formulation or notation of chemical structures.
States. Other important deposits are located in Russia, China,
To illustrate this dilemma, consider the common mineral and
Chile, and Argentina. Table 5 identifies the principal minerals
commercial product, borax. It is usually referred to as sodium
that serve as sources of industrial borates. Over 80% of
tetraborate decahydrate and written as Na2 B4 O7 10H2 O.
the worlds borate production is divided between Turkey
Alternatively, it is often written in the oxide formula,
Na2 O2B2 O3 10H2 O and named sodium(1:2)borate decahy- and the United States. In some cases, minerals, particularly
colemanite and ulexite, are sold directly as commercial
drate. Finally, the structural formula Na2 [B4 O5 (OH)4 ]8H2 O,
or sodium tetraborate octahydrate, is used on the basis of products after minimal refining steps that might include
the actual structure of this compound, which contains the crushing, grinding, and blending. Major uses for these
tetraborate anion (5). beneficiated minerals are in the manufacture of fiberglass
The sodium tetraborate decahydrate system is used almost and ceramics, and as raw materials for the production of
exclusively in commerce, the oxide system in classical boric acid and other boron-containing products. Table 6
mineralogy, and the more correct structural designation in lists the quantities of the principal minerals being mined
chemical discussions. The Chemical Abstract Service (CAS) worldwide.49
has devised another more computer-compatible system for
inorganic borates based on hypothetical acid salts. The CAS 4.3 Sodium Tetraborates
system is not used except in indexing by that reference source.
The metal salt names are used commonly for refined products, Four sodium tetraborates are important as boron minerals
for example, sodium tetraborate decahydrate for borax. The and/or large tonnage items of commerce. Borax, or sodium
problem with this nomenclature is that it is based on the tetraborate decahydrate, is extracted from large open-pit
fictitious [B4 O7 ]2 ion, gives an incorrect count for waters of mines in Turkey and the United States. Turkish beneficiated
hydration, and does not recognize the presence of hydroxyl native borax, also referred to by the mineral name tincal,
groups. This is also true of the oxide formulas, which are is used directly in glass making and other applications.
often used for mineral and glass compositions. The structural Refined borax is used widely in consumer products and as
a starting material for the manufacture of other chemicals. 4.4 Other Sodium Borates
Sodium tetraborate pentahydrate, also known as the mineral
Four additional sodium borates are produced commercially
tincalconite, is produced by recrystallization of borax above
in smaller quantities. So-called disodium octaborate tetrahy-
approximately 60.8 C, and is the boron compound sold in
drate is a commercial product having the hypothetical formula
the largest quantities worldwide. Sometimes referred to as Na2 B8 O13 4H2 O. This is not a discrete crystalline compound
borax pentahydrate, this is the borate product produced in but rather an amorphous spray-dried material having an
the largest tonnage worldwide. Its largest use is in the approximate composition in agreement with this chemical
manufacture of insulation fiberglass. The crystal structures formula. It has a little crystalline character and dissolves
of sodium tetraborate pentahydrate and decahydrates are rapidly in water without the temperature decrease that nor-
both based on the tetraborate ion (5), with three and eight mally occurs when crystalline sodium borates are dissolved. It
molecules of water of hydration respectively. A single-crystal also readily forms supersaturated solutions in hot water. The
X-ray analysis shows that the pentahydrate contains only ratio of sodium to boron in this material is such that maxi-
4.67 equivalent waters of hydration because two of the three mum solubility is achieved. Table 8 illustrates the increased
hydration sites in its structure are only partially occupied.50 solubility of disodium octaborate tetrahydrate compared to
The structural formula of the pentahydrate is therefore borax or sodium borate decahydrate and the magnitude of the
Na2 [B4 O5 (OH)4 ]2.67H2 O, and the common and the oxide supersaturation observed. Disodium octaborate tetrahydrate is
formulas are Na2 B4 O7 4.67H2 O and Na2 O2B2 O3 4.67H2 O marketed under various trade names depending on intended
respectively. use. Major uses of this product are as a boron source in agri-
The oxide formula of the mineral kernite, Na2 B4 O7 4H2 O, culture, a diffusible wood preservative, a flame retardant for
gives the impression that it contains the same tetraborate cellulosic materials, and for the control of insect pests.
structure as sodium tetraborate penta- and decahydrates, but
its actual structure is quite different. Kernite has the structural
formula Na2 [B4 O6 (OH)2 ]3H2 O and contains an anionic Table 7 Aqueous solubilities of some alkali metal and ammonium
borates
borate structural unit consisting of infinite parallel chains
of composition [B4 O6 (OH)2 ]n 2n (7), made up of triborate Compound O C 20 C 40 C 60 C 100 C
rings linked through shared tetrahedral boron atoms.51 The
relatively slow dissolving and crystallization rates of kernite Na2 O5B2 O3 10H2 O 5.77 10.55 17.50 26.88 51.0
Na2 O2B2 O3 10H2 O 1.18 2.58 6.00 15.90
are consistent with this polymeric structure. Kernite is mined Na2 O2B2 O3 4.67H2 Oa 16.40 34.63
in the United States and converted to boric acid. Kernite can Na2 O2B2 O3 4H2 Ob 14.82 28.22
also be hydrated to borax decahydrate and refined into borax Na2 OB2 O3 8H2 Oc 14.5 20.0 27.9
pentahydrate. Na2 OB2 O3 4H2 O 38.3 52.4
Anhydrous sodium tetraborate can exist in several crystal K2 O5B2 O3 8H2 O 1.56 2.82 5.12 9.05 22.3
K2 O2B2 O3 4H2 O 12.1 19.4 28.4 48.4
forms but it most commonly occurs as a glassy amorphous Li2 O2B2 O3 4H2 O 2.2 2.81 3.26 3.76 5.17
product that is used in fused glasses and related products. (NH4 )2 O2B2 O3 4H2 O 3.75 7.63 15.8 27.2
The commercial compound is prepared by fusing sodium (NH4 )2 O5B2 O3 8H2 O 4.00 7.07 11.4 18.2
tetraborate hydrates in a furnace. The resulting melt is pressed a
Commonly known as the pentahydrate, transition point to
between chilled rollers to produce sheets of glassy product decahydrate at 60.7 C, 16.6 wt% Na2 B4 O7 . b Transition point to
that is ground, screened to appropriate sized granules, and decahydrate at 58.2 C, 14.55 wt% Na2 B4 O7 . c Transition point to
packaged for sale. tetrahydrate at 53.6 C, 36.9 wt% Na2 B4 O7 .
BORON: INORGANIC CHEMISTRY 13
4.6 Other Alkali Metal Borates 25 C. The related mineral probertite, NaCaB5 O9 5H2 O or
Na2 O2CaO 5B2 O3 10H2 O, is less common than ulexite. Its
Although potassium and lithium borates are produced com- crystals are monoclinic and have a specific gravity of 2.1.
mercially, their usage is small compared to sodium and cal- It has the structural formula, NaCa[B5 O6 (OH)4 ]3H2 O based
cium borates. Potassium tetraborate, K2 [B4 O5 (OH)4 ]2H2 O on a polymeric pentaborate anionic structural unit.55 Both
(K2 B4 O7 4H2 O), and pentaborate, K[B5 O6 (OH)4 ]4H2 O colemanite and ulexite are mined in large tonnages in Turkey
(KB5 O8 4H2 O), have the same borate anions as found in and sold as impure concentrates for use worldwide in the
the corresponding crystalline sodium borates (5 and 3, respec- manufacture of textile and insulation fiberglass. Colemanite is
tively). When the tetraborate is heated, reversible water loss also used in the manufacture of ceramic glazes. Ulexite ores
begins between 85 and 111 C. Thermogravimetric analysis are also produced in South America and used as a raw material
shows that two moles of water are lost by 140 C, one more for the production of boric acid.
at 200 230 C, and the last one at 250 290 C. Potassium
pentaborate tetrahydrate is stable in a vacuum to 105 C and
up to 170 C in an atmosphere saturated with water at 90 C. 4.8 Zinc Borates
Lithium tetraborate, Li2 [B4 O5 (OH)4 H2 O] (Li2 B4 O7 3H2 O),
and lithium metaborate, Li[B(OH)4 ] (LiBO2 2H2 O), are man- The industrial importance of the zinc borates has
ufactured in relatively small quantities. increased in recent years. Several unique crystalline
Single crystals of anhydrous lithium borates are grown hydrated zinc borates are known, exhibiting a range
from high-temperature molten salt for use in optoelectronic of structure types illustrative of the diversity of borate
devices. Crystalline anhydrous lithium triborate, LiB3 O5 , is chemistry. Well substantiated crystalline zinc borates have the
used commercially as a nonlinear optical material to con- compositions 4ZnOB2 O3 H2 O,5659 ZnOB2 O3 1.12H2 O,60
vert light from high-powered lasers from higher to lower ZnOB2 O3 2H2 O (or 2ZnO2B2 O3 3H2 O), 6ZnO5B2 O3
frequencies. Its attributes in this application include a wide 3H2 O,61 2ZnO3B2 O3 7H2 O,62 2ZnO3B2 O3 3H2 O,57 2ZnO
transparency range and high-damage threshold. Crystalline 3B2 O3 9H2 O (or 3ZnO5B2 O3 14H2 O), and ZnO5B2 O3
anhydrous lithium tetraborate, Li2 B4 O7 , is used as a piezo- 4.5H2 O,61 spanning a range of B2 O3 :ZnO mole ratios from
electric material in mobile communications devices such as 0.25 to 5. Each of these compounds can be prepared selectively
cellular phones and pagers. by aqueous reactions of zinc oxide with boric acid, or
by reactions of zinc and borate salts, with the specific
compound obtained determined by reactant concentrations and
4.7 Calcium Borates temperature. Only 4ZnOB2 O3 H2 O, ZnOB2 O3 1.12H2 O,
2ZnO3B2 O3 7H2 O, and 2ZnO3B2 O3 3H2 O have been
A number of crystalline calcium borates are known structurally characterized, and compositions of the remaining
that occur as either minerals or synthetic compounds. four should be considered approximate until their structures
The most important calcium borate mineral is colemanite, are elucidated. The compound 4ZnOB2 O3 H2 O has the
2CaO3B2 O3 5H2 O. This mineral exists in nature as structural formula Zn2 (BO3 )OH and consists of corrugated
monoclinic crystals having a specific gravity of 2.42. sheets of oxygen-sharing ZnO3 OH tetrahedra interconnected
Colemanite contains polymeric chains of the triborate by BO3 triangles into an infinite network.58,59 This structure
anion [B3 O4 (OH)3 ]n 2n .53 At 480 C, colemanite decrepitates is noncentrosymmetric as first shown some years after
violently, losing all of its water and forming a low-bulk density this compound had become a commercial product, by the
powder. The water solubility of colemanite is relatively low structure determination of the closely related OH/F disordered
for a borate, 0.1 wt% at 25 C and 0.38 wt% at 100 C. compound Zn2 (BO3 )(OH)0.75 F0.25 , which gives essentially
A second important calcium borate is the mineral the same X-ray pattern.59 The compound ZnOB2 O3 1.12H2 O
ulexite, NaCaB5 O9 8H2 O or Na2 O2CaO5B2 O3 16H2 O. It consists of a complex extended network of unusual, large
can also be prepared synthetically by seeding an aqueous B12 O24 12 polycyclic borate units interconnected by cationic
solution of calcium metaborate, boric acid, borax, and Zn3 O3 clusters into an infinite network.60 This results in
probertite, NaCaB5 O9 5H2 O. Ulexite crystals are triclinic an open framework solid containing one water molecule
with a specific gravity of 1.95. When ulexite is heated, coordinated to each zinc atom as well as some additional
four moles of water are lost at 80 100 C, 8.5 more at interstitial water. The compound 2ZnO3B2 O3 7H2 O has the
175 C, and the remaining 3.5 moles at 450 C. Ulexite has the structural formula Zn[B3 O3 (OH)5 ]H2 O, and contains isolated
structural formula NaCa[B5 O6 (OH)6 ]5H2 O and contains the [B3 O3 (OH)5 ]2 anions.62 The compound 2ZnO3B2 O3 3H2 O
pentaborate trianion.54 This anion is similar to (3) with two has the structural formula Zn[B3 O3 (OH)5 ]H2 O, and contains
additional hydroxyl groups bound to two of the trigonal borons infinite chains of triborate rings similar to those found in
making them tetrahedral. An unusual property of some ulexite the calcium borate mineral colemanite, interconnected by
crystals is their ability to behave as fiber optic material and coordination with zinc (9).57
project images through the crystals in one direction. Ulexite A few zinc borates are currently manufactured in significant
has a relatively low water solubility, 0.5 wt% as NaB5 O9 at tonnages. Most of the zinc borates listed above have
BORON: INORGANIC CHEMISTRY 15
ammonioborite. This compound contains the unusual 15- 6 BORIC ACID ESTERS
boron anion, [B15 O20 (OH)8 ]3 (10), produced by the formal
condensation of three pentaborate anions (3). Another ammo-
nium borate mineral, larderellite, [NH4 ][B5 O7 (OH)2 ]H2 O, 6.1 Introduction
contains an anionic structural unit composed of an infinite
Ebelman and Bouquet prepared the first examples of boric
chain of condensed pentaborate anions (11). Both the isolated
acid esters in 1846 from boron trichloride and alcohols.70
trianion (10) in ammonioborite and the chain polyanions (11)
Literature reviews of this subject are available.71,72 The
in larderellite are so far known to occur only with the ammo-
general class of boric acid esters includes the more common
nium cation.
orthoboric acid based trialkoxy- and triaryloxyboranes,
B(OR)3 (1), and also the cyclic boroxins, (ROBO)3 , which
3
HO OH HO are based on metaboric acid (2). The boranes can be simple
B O O
O B B O trialkoxyboranes, cyclic diol derivatives, or more complex
B B B OH trigonal and tetrahedral derivatives of polyhydric alcohols.
O O O
O O B O Nomenclature is confusing in boric acid ester chemistry. Many
O B O O B
O O O trialkoxy- and triaryloxyboranes such as methyl, ethyl, and
HO B B B
B B O O B phenyl are commonly referred to simply as methyl, ethyl, and
O O
OH HO OH phenyl borates. The IUPAC boron nomenclature committee
has recommended the use of trialkoxy- and triaryloxyboranes
(10)
for these compounds, but they are referred to in the literature
as boric acid esters, trialkoxy and triaryloxy borates, trialkyl
HO
n and triaryl borates or orthoborates, and boron alkoxides and
O
B B aryloxides. The IUPAC nomenclature will be used in this
O O review except for relatively common compounds such as
B methyl borate. Boroxins are also referred to as metaborates
O O
and more commonly as boroxines. Boroxin is preferred by
B B the IUPAC nomenclature committee and will be used in this
O O OH
n review.
(11)
the demanding steric requirements of the sp3 hybridized is approximately planar, generally exhibiting a small out-
transition state formed when the boron center undergoes a of-plane envelope deformation. The trigonal boron atoms
nucleophilic attack by water. Compounds that have internal in trialkoxyboroxins generally exhibit a stronger Lewis acid
coordination to boron, for example, the transannular bond character than comparable borons in trialkoxyboranes because
from the electron pair on nitrogen to boron in compounds there is only one electron-donating alkoxy group per boron.
such as tripropanolamine borate (14) and triethanolamine Preparative methods are essentially the same as those noted for
borane (15), exhibit good hydrolytic stability. Owing to lower trialkoxyboranes except that the stoichiometry is changed. The
ring strain, tripropanolamine borate is more resistant to calcium hydride method is particularly efficient for prepara-
hydrolysis than triethanolamine borate. Some comparative tion of boroxins, which are difficult to prepare using azeotropic
hydrolysis rates in homogeneous water-dioxane are shown distillation. Although some boroxins have been offered com-
in Table 10.74 Reactions were run either at 21 C in 60% mercially, no significant applications for them have been
dioxane or at 55 C in 91% dioxane, and the relative developed.
rates adjusted to comparable values are shown in the
table.
6.4 Esters of Polyhydroxy Compounds
Other reported binary boron sulfides include subvalent is more difficult than the corresponding BO bonds, and
B12 S, a black crystalline material prepared by a high- nucleophilic displacement of RS groups proceeds more readily
temperature reaction of amorphous boron with elemental than with RO groups upon attack by nucleophiles such as
sulfur, and BS, which has been studied spectroscopically in an water, alcohols, and amines. Exchange reactions with thiols
electric discharge. A vapor-phase dimer, (BS)2 , was identified, also proceed readily, and these reactions can be used to prepare
and a refractory condensed form of BS was reported from the thioborates of higher boiling thiols (equation 14). Although a
reaction of elemental boron with sulfur at 1850 C and a sulfur analog of boric acid has not been reported, the cyclic
pressure of 94 500 atmospheres. Boron disulfide, BS2 , has metaboric acid (1) analog, (HSBS)3 , has been characterized.
been identified in the gas phase and appears to be the primary The dimer (HSBS)2 was also isolated and shown to readily
compound present in the vapor phase over diboron trisulfide convert to the trimer on heating.
or elemental boron and sulfur.
B(SR)3 + 3HSR B(SR )3 + 3RSH (14)
some stable derivatives of the type R2 PBR2 , where R and 9.2 Boron Trihalides
R are bulky groups, have been isolated. The six-membered
rings in phosphinoborane trimers and eight-membered rings in 9.2.1 Properties
tetramers consist of alternating boron and phosphorus atoms
with some out-of-plane puckering of the rings. These cyclic A chronology of the discovery and characterization of the
compounds are colorless crystalline solids having thermal four boron trihalides is interesting since the scientists involved
stability. The P -hexamethyl trimer, for example, is stable were some of the most prominent chemists of the 19th century:
to 250 C in vacuum. However, decomposition is rapid in
the presence of air. The boron hydrogen bonds in these 1809 boron trifluoride Davy, Gay-Lussac, Thenard
compounds are unexpectedly resistant to hydrolysis. The 1824 boron trichloride Berzelius
hypothetical compound (HPBH)3 , the phosphorus analog of 1846 boron tribromide Poggiale
the common boron nitrogen trimer borazine, has not been 1891 boron triiodide Moissan
isolated. However, derivatives of this compound containing
the six-membered (PB)3 moiety can be stabilized using bulky
substituents on the boron and phosphorus atoms, as in (2,4,6- Boron trihalides were studied extensively in subsequent
Me3 C6 H2 BPC6 H11 )3 .85 years, and their chemistry has been summarized in several
Boron phosphate, BPO4 , is prepared by the dehydration of reviews.8688 They are also referred to as trihaloboranes, but
a mixture of boric acid and phosphoric acid at temperatures boron trihalide is used more frequently. Boron trihalides are
of 1000 1200 C. Although BPO4 begins to form in these trigonal molecules with bond angles of the expected 120 .
mixtures at much lower temperatures, complete dehydration This sp2 hybridized state leaves a vacant 2pz orbital on
requires temperatures above 1000 C. Boron phosphate is a boron, a characteristic that, as with other boron compounds,
white infusible solid that slowly vaporizes above 1450 C provides the basis for much of the chemistry of boron
without decomposition. The structure of boron phosphate halides. The measured bond lengths in boron trihalides are
prepared under atmospheric conditions consists of tetragonal shorter than calculated, and their Lewis acidities (BI3 >
bipyramids analogous to the high cristobalite forms of BBr3 > BC13 > BF3 ) are reversed from the order expected
silica. Both boron and phosphorous atoms are tetrahedrally from a consideration of the relative electronegativities of
coordinated by oxygen. Heating the common form of boron the halogens. For example, boron trifluoride is the weakest
phosphate to 500 C at 5 GPa (50 000 atm) yields a quartz-like acceptor with electron donors such as amines even though
form. A number of hydrates of boron phosphate have been fluorine is the most electronegative of the halogen substituents.
prepared: BPO4 nH2 O where n = 3, 4, 5, or 6. All the hydrates These observations are usually rationalized by assuming back-
decompose in water to give the parent acids; anhydrous bonding in which nonbonding halogen electrons interact with
boron phosphate hydrolyzes similarly. The anhydride is used the vacant p orbital on boron. If this does occur to a significant
as a heterogeneous catalyst. The related compound, boron extent, fluoride would be the most effective back-bonding
thiophosphate, BPS, is prepared by reaction of the elements halogen and iodide the least, thereby rationalizing the observed
or from diboron trisulfide, phosphorus, and sulfur. order of Lewis acidity and the unexpectedly short bond lengths
observed in all the trihalides. This presumed bonding order
was confirmed experimentally in investigations of gas-phase
photolysis spectra of boron trihalides.89
Table 11 outlines some physical properties of the trihalides
9 BORON-HALOGEN COMPOUNDS including bond lengths and bond energies. Each property
tends to vary continuously from gaseous boron trifluoride to
the relatively high-boiling boron triiodide. All of the pure
9.1 Introduction compounds are colorless, although the bromide and iodide
become colored when exposed to light, apparently as the
Boron-halogen compounds, or boron halides, can be result of photolytic liberation of the free halogens.
divided into three major categories that are defined by the
ratios of halogens to borons. The boron trihalides (halo-
gen:boron ratio = 3) were discovered and characterized first Table 11 Physical properties of boron trihalides
and represent the most common and thoroughly investigated
Property BF3 BCl3 BBr3 BI3
boron halide category. Haloborates, with a halogen:boron
ratio of 4, are important because of the relatively widespread Mp ( C) 127.1 107 46 49.9
commercial usage of fluoroborates. The third category, boron Bp ( C) 99.9 12.5 91.3 210
B-X Bond length, A 1.30 1.75 1.87 2.10
subhalides, with halogen:boron ratios <3, represents a theoret-
B-X Bond Energy, kJ mol1 646 444 368 267
ically interesting class of compounds that have been prepared
only in relatively small quantities. Note: X = halogen.
22 BORON: INORGANIC CHEMISTRY
9.2.2 Preparation and Uses If the donor molecule contains reactive hydrogen, as H2 O,
NH3 , PH3 , AsH3 , R2 NH, RNH2 , and lower alcohols, hydrogen
Boron Trifluoride. Boron trifluoride is prepared commer- halides are produced (equations 17 19). In these reactions the
cially by the reaction of fluorosulfonic acid (HSO3 F) with initial adducts formed with boron trifluoride are much more
boric acid in sulfuric acid followed by purification using stable to protonolysis than with the other trihalides, and these
fractional distillation. It can also be prepared by the reac- reactions proceed slowly or not at all.
tion of fluorspar (CaF2 ) with boric acid or its equivalent,
borax (Na2 B4 O7 10H2 O) and sulfuric acid, or by the two-step BX3 + H2 O B(OH)3 + 3HX (17)
reaction of borax with hydrofluoric acid and sulfuric acid.
BX3 + R2 NH (R2 N)3 B + 3HX (18)
Various other methods have been reported for laboratory-
scale synthesis or preparation of high-purity boron trifluoride. BX3 + 3ROH (RO)3 B + 3HX (19)
One example of a procedure for preparation of high-purity
material is thermal decomposition of benzenediazonium fluo- Some of these reactions, particularly with the strongest
roborate. Boron trifluoride is used in significant quantities as Lewis acids, are rapid or even violent at room temperature. In
a Lewis acid catalyst in the large-scale production of organic general, boron trifluoride is significantly less reactive than the
compounds, particularly in Friedel-Craft reactions, and as an other halides. For example, it forms two distinct hydrates that
epoxy resin curing agent. In this application, boron trifluoride are stable to 20 C. This resistance to hydrolysis and strong
is either used directly, as one of its coordination compounds, Lewis acid character has led to the relatively wide use of
or mixed with a promoter. Distillation of the dimethyl etherate boron trifluoride as a reaction catalyst in a number of organic
of boron trifluoride is used commercially for the separation reactions.
of 10 B and 11 B isotopes and the subsequent production of Exchange reactions are common between boron halides and
isotopically enriched boron compounds. alkyl or aryl substituents, other halides, alkoxy and aryloxy
groups, and diborane. Some examples are shown in Scheme 2.
Boron Trichloride. Boron trichloride is prepared com- Reduction of boron trihalides to elemental boron can be
mercially by the chlorination of boron carbide (equation 15). accomplished by heating with alkali metals, alkaline earth
Direct chlorination of boric acid or a sodium borate in the metals, or hydrogen. Under the proper conditions, reductions
presence of carbon is an alternative method. Most of the boron of this type can also yield diborane and, under selected
trichloride produced is converted to filaments of elemental conditions, boron subhalides (see below). Metal hydrides also
boron by chemical vapor deposition (CVD) on tungsten wire react with boron trihalides to give diborane. Boron nitride and
in a hydrogen atmosphere. Numerous laboratory preparations boron carbide have been prepared by the high-temperature
of boron trichloride have been reported. One of the most con- reductions of boron trihalides with ammonia and methane,
venient is the halogen exchange reaction of aluminum chloride respectively, and deposited on metal substrates by CVD.
with boron trifluoride or a metal fluoroborate.
and FBF angles close to the theoretical 109 . It is a strong with boron:halogen ratios of 1. These compounds are
acid in water with a pK of 4.9 compared to 4.3 for structurally analogous to the polyhedral boranes (see Boron
nitric acid. Hydrides), but exhibit significant differences in reactivity
Fluoroboric acid is produced commercially by the reaction and other properties. The polyhedral boron hydrides are
of 70% hydrofluoric acid with boric acid. Fluoroborate colorless liquids or white solids, whereas many polyhedral
solutions must be treated like hydrofluoric acid and handled perhaloboranes are intensely colored, ranging from yellow
in corrosion resistant equipment consisting of polyethylene, to purple and black. The simplest polyhedral derivative
polypropylene, or neoprene-type rubber. The major use of is tetraboron tetrachloride, B4 Cl4 , which has tetrahedral
fluoroboric acid is as an intermediate in the preparation of geometry. This yellow solid is also prepared using radio
fluoroborate salts. It is also used in electroplating aluminum frequency discharge syntheses. The bromide and the mixed
and in metal cleaning operations. chlorobromo derivatives can be prepared by the exchange
Metal fluoroborates are produced either from fluoroboric reaction of diboron tetrachloride with boron tribromide. Larger
acid and metal salts or by reactions of boric acid and polyhedral perhaloboranes, including Bn Cln (n = 8 12) and
hydrofluoric acid with metal salts. Fluoroborates of alkali Bn Brn (n = 7 10) have been described. Although structures
metals and ammonium ions tend to crystallize as hydrates and have yet to be determined for all of the Bn Xn clusters, it
are water soluble except for those of potassium, rubidium, is clear that most of them do not conform to the electron
and cesium. The major use for these compounds is as a counting rules to which the polyhedral boron hydrides and
high-temperature flux. Transition metal and other heavy metal many other inorganic cluster systems generally adhere. For
fluoroborates are not as well known and well characterized. example, the structure of B8 Cl8 is that of a regular closed 8-
They are usually prepared from fluoroboric acid and an vertex polyhedron, yet this compound has only 2n framework
appropriate salt and are sold as 40 50% water solutions. electrons (for n vertices), rather than 2n + 2 framework
Some fluoroborates from metals such as tin, lead, copper, and electrons stipulated by electron counting formalisms. The
nickel are prepared by electrolysis of fluoroboric acid. The structures of several boron subfluorides, including B8 F12 and
transition and other heavy metal fluoroborate solutions are B10 F12 , were recently determined revealing unusual open
used primarily as plating solutions and catalysts. structures.92 The chemistry of boron subhalide compounds
remains an area of academic research interest.
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Boron: the sandwich compound (2). Structure (1) emphasizes that the
iron atom is an integral part of [Fe(C2 B9 H11 )2 ]n , while (2)
Metallacarbaboranes shows that [Fe(C2 B9 H11 )2 ]n can be considered as consisting
of two nido-carbaborane clusters, each of which behaves as
an 5 ligand to the Fe(II) or Fe(III) center. The [C2 B9 H11 ]2
Catherine E. Housecroft (dicarbollide) ligand (3a) behaves in a similar fashion to a Cp
University of Basel, Basel, Switzerland ligand (3b)2 and, therefore, a parallel can be drawn between
the iron(II) metallacarbaborane [Fe(C2 B9 H11 )2 ]2 and the
organometallic -complex FeCp2 (ferrocene). Despite the
apparent analogy between [C2 B9 H11 ]2 and Cp , experimen-
1 Introduction 1 tal observations indicate that metallacarbaboranes are often
2 Classes of Compound and Geometrical Aspects 2 more stable than their metallocene analogs. The carbaborane
3 Bonding 8 units are typically robust, and metallacarbaborane chemistry
4 Synthesis 9 is generally more extensive than metallocene chemistry.
5 Skeletal Isomerism 13
6 Electrochemistry 15
7 Reactivity 15 n n
8 Applications 17 B B
9 Future Ways Forward 19
B B B B B B B B
10 Related Articles 20 B B
11 References 20
B B
B B B B
C C C C
Fe Fe
C C C C
B B B B
Abbreviations B B
B B
H2 OEP = Octaethylporphyrin; PPN = Bis(triphenylphos- B B B B
B B B B
phino)iminium(1+); PSEPT = Polyhedral skeletal electron
pair theory; TMEDA = N ,N ,N ,N -Tetramethylethylene- B B
diamine; nbd = Norbornadiene; cod = 1,5-Cyclooctadiene. B = BH, C = CH, n = 1, 2 B = BH, C = CH, n = 1, 2
(1) (2)
Glossary
2
B C C B
Metallacarbaborane (also called metallacarborane): an B
electron-deficient compound, usually a polyhedral cluster
B
comprising an array of boron hydride (BH), carbon hydride B B
B B
(CH), and metal (MLx , where L = ligand) fragments; the
inclusion of a substituted carbon fragment CR (R = alkyl, B
aryl, or trimethylsilyl) in place of a CH unit is common B = BH, C = CH
(3a) (3b)
1 1 2 1
1
4
5 5 6
4 2 4 6 5
2 4 2 3
3 3 3
8
5 6 7
7
Trigonal Pentagonal
bipyramid Octahedron bipyramid Dodecahedron
1
5
1 1
5
8 9 4 2 6
3 3 2 5 2
7 4
2 3 4 3
8 6 5
7 9
7 6 10 11
4 6 9 8
10 9 7
1 8
11
10 12
Tricapped Bicapped
trigonal prism square-antiprism Octadecahedron Icosahedron
Figure 1 Closed deltahedra (polyhedra with triangular faces) with 5 12 vertices and the IUPAC numbering system for each cage. The
structures of most metallacarbaboranes are based on or derived from these eight deltahedra
is especially well developed for icosahedral and pentagonal vertices removed), and commo (a structure derived from the
bipyramidal cages (see Figure 1), and it has progressed from fusion of, for example, two deltahedra sharing a common
the inclusion of d-block metal atoms to main group9,10 and vertex).
f-block6,11,12 metal atoms.
Three general reference works cover metallacarbabo-
rane chemistry in a systematic manner up to around
2005,46 and several books include articles covering topical 2 CLASSES OF COMPOUND AND GEOMETRICAL
developments.1316 Annual reports17 have surveyed advances ASPECTS
in the subject since 1971, and continue to do so.
Details of the preliminary IUPAC nomenclature for
metallacarbaborane clusters are described in the 1990 2.1 Single Cages
recommendations.18 However, care is needed in interpreting In a single-cage metallacarbaborane, the cluster skele-
compound names in the literature. Over the years, there has ton consists of one complete polyhedron or one polyhedral
been some variation with respect to the order in which boron, fragment. Examples of closo-metallacarbaboranes in which
carbon, and metal atoms are numbered in a given cluster. one metal fragment has replaced a BH unit in the carbab-
An example is (4), which is described as 3-Cp-3-Fe-1,2- orane 1,2-C2 B10 H12 are CpFeC2 B9 H11 (4), CpCoC2 B9 H11 ,
C2 B10 H12 by the IUPAC 1990 recommendations, but is also (OC)3 RhC2 B9 H11 , and [(OC)3 MoC2 B9 H11 ]2 . Each of these
found in the literature as 3-(CpFe)-1,2-C2 B10 H12 , 1-Cp-1-Fe- compounds adopts an icosahedral framework. Many met-
2,3-C2 B10 H12 , or 1-(CpFe)-2,3-C2 B10 H12 . allacarbaborane clusters with closed-cage structures smaller
Most of the structures of metallacarbaborane clusters derive than the icosahedron are known, for example, the 11-vertex
from triangular-faced polyhedra. Figure 1 shows regular closo-1-(6 -MeC6 H4 -4-i-Pr)-2,3-Me2 -1-Ru-2,3-C2 B8 H8 (5).
deltahedra up to the icosahedron with the corresponding A large group of metallacarbaboranes adopts the closo-C2 B4 M
IUPAC vertex numbering schemes. General cluster classes are core and each possesses a pentagonal bipyramidal structure,
closo (a complete deltahedral structure), nido (a deltahedron for example, 1-Cp Co-2,3-C2 B4 H6 (6), 1-Ge-2,3-(SiMe3 )2 -
with one vertex vacant), arachno (a deltahedron with two 2,3-C2 B4 H4 (7), and 1-Fe(CO)3 -2,4-C2 B4 H6 (8).
BORON: METALLACARBABORANES 3
Me L1
L2
H
M C C B
Fe i -Pr Ru
B
B B L1
B C C C
C B
B B B B
B B B B B
B B
B B B B
B
B
B B
(9) B = BH, C = CH, M = Pt, L1 = PEt3, L2 = H
B = BH, C = CH B = BH, C = CH
(10) B = BH, C = CH, M = Rh, L1 = L2 = PMe3
(4) (5)
Ph3P
H
C Pt PPh3
B B
Ge H
Co
B B
B B C B B B
C B
C C B B
B
B B B
B = BH, C = CH B = BH, C = C(SiMe3) B = BH, C = CH2
(6) (7) (11)
CO
OC CO 2.2 Sandwich Complexes
Fe
The open face of nido-[C2 B9 H11 ]2 may behave in a
C B B B similar manner to a cyclopentadienyl ring (see Section 1)
C
and coordinate to Mn+ to give sandwich complexes such
B as commo-[Fe(C2 B9 H11 )2 ]n (n = 1 or 2), (1) and (2).
B = BH, C = CH Related clusters are the chromium(III) complex commo-
(8) [Cr(C2 B9 H11 )2 ] and the nickel(IV) complex Ni(C2 B9 H11 )2 .
In f-block metal complexes, the higher coordination num-
bers of the metal center lead to the addition of halide or
The number of metallaboranes and metallacarbaboranes solvent ligands and a concomitant tilting of the carboranyl
in which the metal is from the s block has grown over the ligands, for example, in [(C2 B9 H11 )2 MX2 ]2 (M = U, Th;
past two decades,1921 but is still not large when compared X = halide) (see below).26,27 Mixed metallacarbaborane/ -
to metallacarbaboranes incorporating d-block metal cen- organometallic complexes such as (4) may also be recognized
ters. Single-cage metallacarbaboranes include closo-1,1,1,1- as sandwich molecules. Similarly, the zirconium(IV) metal-
(MeCN)4 -1,2,4-CaC2 B10 H12 ,22 (closo-1,1,1-(MeCN)3 -1,2,4- loporphyrin carbaborane compound (OEP)Zr(C2 B9 H11 ) (12)
SrC2 B10 H12 )n ,23 and closo-1-Mg(TMEDA)-2,3-(SiMe3 )2 - can be classed as a sandwich complex.28
2,3-C2 B4 H4 .24 Group 1 metal ions are often associated through Like nido-[C2 B9 H11 ]2 , the dianion nido-[C2 R2 B4 H4 ]2
interactions to the outside of the cage rather than being (R = H, Me, SiMe3 ) exhibits an open pentagonal face, and
part of the skeleton of the cluster. An example, in which the frontier orbitals of the two nido-carbaborane anions are
M+ participates in both the roles, is [exo-Cs(TMEDA)-1- similar. Thus, it is not surprising to find complexes of the type
Cs-(SiMe3 )4 C4 B8 H8 ]n .25 Metallacarbaborane clusters incor- commo-Ge{2,3-(SiMe3 )2 -2,3-C2 B4 H4 }2 (13) and commo-
porating f-block metal atoms are actively being developed, and FeH2 (2,3-Me2 -2,3-C2 B4 H4 )2 (14) in which the pentagonal
the last 15 years have seen a significant growth in this area.11,12 faces of the two nido-carbaborane ligands are parallel to one
Large numbers of metallacarbaboranes in which the metal another. The tin(IV) complex commo-Sn{2-(SiMe3 )-3-Me-
atom effectively closes an otherwise open carbaborane cluster 2,3-C2 B4 H4 }2 (15) adopts a bent-sandwich structure, with the
are known. However, there are also many compounds in which two C2 B3 rings subtending an angle of 142.5 at the metal
the metal fragment occupies a site in an open (nido or arachno) center. This observation is of interest in view of the bent
polyhedral cage, for example, nido clusters (9 11). geometries observed for the stannocenes Cp2 Sn and Cp 2 Sn.
4 BORON: METALLACARBABORANES
Zr
B B
B B B B
N N B B C B
B B
B B B C
N N B B
C B
C Sm B
B = BH, C = CH O O
(12)
B = BH, C = CH
B B (16)
2
B B B B
C B B B B B B B
C B C C
C C
B B B B
Ge H Fe H B B
B B B B
B C
B C B C C B
B C B C B Eu B
B B
B B O O
B B
S B C B C
B C C B
N
HC + CoIII Ni
Co Co
N
C C
S B
B
C B B C C B B B B C C
B B C B B
B B
B B B
B B B B B B B
B B
B = BH, C = CH B = BH, C = CH
(18) (19) B B
B B
C C B B B B C C
2.3 Stacked Complexes
Co Co
B B B B B
Au B B
Fe B B B
C C
B B B B C B
B
C B
B
B = BH, C = CMe B = BH, C = CEt
B = BH, C = CH
(20) (21) (23)
6 BORON: METALLACARBABORANES
shorter than the M B distances (Cr Bav = 232.1 pm and Table 1 Structural data to illustrate the interaction of Tl(I) with
Cr Cav = 217.9 pm). the C2 B3 open face of the [1,2-R2 -1,2-C2 B9 H9 ] ligand in
[X][1,2-R2 -3-Tl-1,2-C2 B9 H9 ](a)
In single-cage closo-metallacarbaboranes containing a
main group metal atom, the slippage of the heteroatom X R Tl B (pm) Tl C (pm)
with respect to the open face of a nido-[C2 B9 H11 ]2 or
nido-[C2 B4 H6 ]2 ligand, or C-substituted analogs of these Tl Me 273.9(82), 268.2(72), 317.3(73), 327.8(25)
296.9(73)
ligands, is commonly observed.20 In general, interaction PPN H 266.4(7), 274.4(8), 291.5(6), 292.3(6)
with the three boron atoms is greater than that with the 274.1(7)
two carbon atoms. The p-block atom may or may not Ph3 MeP(b) H 274.3(6), 274.1(6), 292.1(5), 291.0(5)
carry a terminal substituent. In cases where a bare metal 265.9(6)
atom is incorporated into the metallacarbaborane cluster, it (a)
may function as a Lewis acid. In 1-Sn-2,3-(SiMe3 )2 -2,3- Distances should be compared with the sums of appropriate
covalent radii: rcov for B = 82, C = 77, Tl = 155 pm. (b) The structure
C2 B4 H4 (24), distances from Sn to the adjacent B and C of the anion is dimeric in the solid state; see (27).
atoms are Sn Bav = 242.8 pm and Sn Cav = 249.8 pm. In
the adduct 1-(bipy)-1-Sn-2,3-(SiMe3 )2 -2,3-C2 B4 H4 (25), not
only is the slip distortion more pronounced than in (24) long, suggesting Tl+ [1,2-C2 B9 H11 ]2 ion pairing. Consis-
(Sn Bav = 248 pm and Sn Cav = 273 pm) but the plane tent with this is the fact that the Tl(I) center is readily
of the donor 2,2 -bipyridine (bipy) molecule is acutely displaced by other metal ions. In the solid state, variation
tilted with respect to the metallacarbaborane cluster core. in the structure of [3-Tl-1,2-R2 -C2 B9 H9 ] (R = H or Me) is
Tilting of terminal substituents or donor molecules is observed as a function of the counterion; slip distortion is
observed in many related metallacarbaboranes, e.g., 1-Me- observed in all cases and is extreme in Tl[3-Tl-1,2-C2 B9 H11 ].
1-Ga-2,3-C2 B4 H6 (26), 1-Me-1-In-2,3-C2 B4 H6 , 1-bipy-1-Sn- Table 1 lists selected structural data for the [3-Tl-1,2-R2 -1,2-
2,3-Me2 -2,3-C2 B9 H9 , 1-THF-1-Sn-2,3-Me2 -2,3-C2 B9 H9 . For C2 B9 H9 ] anion in several salts. In [PPN][3-Tl-1,2-C2 B9 H11 ],
the donor acceptor complexes, the trend is for an increase in dimer formation for the anion (27) is observed in the solid
the slip distortion and a decrease in the tilting of the donor state with an internuclear separation between the symmetry-
ligand as the Lewis acid base interaction becomes stronger. related thallium atoms of 424.1 pm; the dimeric structure is
A number of theoretical studies have addressed the origins of stabilized by B H Tl bridges.46 A novel case of ion pair-
slip distortion.9 ing is exemplified in {[closo-1-Nd(-H)6 -2,4-(SiMe3 )2 -2,4-
C2 B4 H4 ]+ [1,1 -(THF)2 -2,2 ,4,4 -(SiMe3 )4 -5,5 ,6,6 -(-H)4 -
1,1 -commo-Nd(5 -2,4-C2 B4 H4 )] }2 . This complex consists
N of a half-sandwich cationic neodymacarbaborane coordinated
N to an anionic, fully sandwiched neodymacarbaborane.47
Sn Sn
B B B C B B B C
C C
B B B
B = BH, C = C(SiMe3) B = BH, C = C(SiMe3) B H
B B
(24) (25) C
Tl
B B C
pm
H B
Me B B
4.1
Ga B B
42
B H
C B B
B B Tl
B C C
B B
C H B
B B
B = BH, C = CH B = BH, B = B, C = CH
(26) (27)
In most metallacarbaboranes, the interaction between the In the extreme, the slip distortion described above leads
metal atom and carbaborane cage is considered to be essen- to the C2 B3 face of a dicarbollide ligand interacting with a
tially covalent, and this is supported by the experimentally metal atom through only three B atoms. The similarity to an
determined M B and M C distances. However, in [3-Tl-1,2- organometallic allyl complex results in the term borallyl being
C2 B9 H11 ] , the distances from the thallium(I) center to the C used for this type of bonding mode. Examples where the metal
and B atoms in the open face of the C2 B9 cage are particularly binds to only one or two B atoms are also known, that is, M
BORON: METALLACARBABORANES 7
Ph3P B B
B B B B
B B B B
Au
B B
Co B = BH
(30)
C C B B B B B B
B B
H B B
B
B B Hg B B
B B
B B B B
B B B
Cl B B
B B B B
B = BH, C = CH B = BH, C = CH
(28) (29) B B C C B B
B C Hg C B
B B B B
Hg Hg
Copper(I), silver(I), gold(I), and mercury(II) fragments B B
B C C B
exhibit a tendency to bridge the edges of polyhedral clusters I
of various types. In metallacarbaborane clusters, one example B C C B
B B
is (-AuPPh3 )-9-SMe2 -7,8-C2 B9 H10 ; the structure is related Hg Hg
to that of (28) except that the gold(I) unit bridges one B B edge B B B B
B C Hg C B
asymmetrically. The preference is for the metal atom to bridge B B
B C C B
a B B rather than a B C or a C C edge, and this reflects
the observed preferences for bridging H atoms in borane and B B B B
B B B B
carbaborane clusters (see Boron: Polyhedral Carboranes). B B B B
An example of an edge-bridging mercury(II) unit is shown in
B B
(29). In the above examples, the metal atom associates with
the carbaborane polyhedral cage via a boron metal bond. B B
Association through a carbon metal bond is also well Me groups omitted
established. Important precursors to C-substituted derivatives (31)
(not necessarily metallated derivatives) of C2 B10 H12 are
the lithiacarbaborane 1,2-Li2 -1,2-C2 B10 H10 and its 1,7- and 2.7 Exo-metallated Clusters
1,12-isomers (see later). The presence of an M C bond
means that members of this class of metallacarbaboranes In some metallacarbaborane clusters, a metal fragment
can be considered as organometallic complexes. Some of the is supported on the outside of the carbaborane skeleton,
examples are the organomercury complexes Hg4 (C2 B10 H10 )4 typically by B H M interactions, for example, complex (27)
(30)48 and (9,12-Me2 C2 B10 H8 Hg)3 ; the latter reacts with LiI involves exo interactions between the Tl(I) atom of one cage
to give the unusual sandwich complex (31).49 In contrast and two terminal boron hydrogen bonds of a second cage.
to the usual linear coordination environment observed at The exo descriptor illustrates the relationship of the metal
Hg(II), that in Hg4 (C2 B10 H10 )4 (THF)4 2H2 O is nonlinear fragment to the carbaborane and the nido descriptor classifies
(C Hg C = 167.7(8) ). the carbaborane cage.
8 BORON: METALLACARBABORANES
occupy nonbonding orbitals. The FeH2 unit therefore has four {B}. The nonspecific nature of particle aggregation makes
electrons available for cluster bonding, two for each half of the (iv) unattractive in most instances.
commo cluster. This gives a total of 16 electrons (eight pairs)
per half-cluster and so each half-cluster has a closo structure.
Alternatively, if FeH2 (2,3-Me2 -2,3-C2 B4 H4 )2 is similar to a 4.1 Carbaborane Anion with Metal Halide
-organometallic complex, then the 18-electron rule can be The most general synthetic strategy in the preparation of
applied to the Fe atom. Each [(CMe)2 B4 H4 ]2 ligand is a metallacarbaborane clusters is the addition of a metal fragment
6 -electron donor to the Fe(II) center (d6 configuration); in to an anionic carbaborane cluster, that is, {M} + {CB}. Many
this model, the H atoms are counted as protons and provide methods involve the metallic capping of a nido-carbaborane to
no electrons. A neutral-atom model can also be adopted in generate a closo-metallacarbaborane. The examples given in
which each neutral (CMe)2 B4 H4 unit is a 4 -electron donor equations (3 6) illustrate cases in which the electron count for
to the Fe(0) center (s2 d6 configuration). In this model, each H the cluster remains unaltered during the reaction and hence the
atom provides one electron to the Fe(0) atom. Either way, the polyhedral skeleton of the closo product is related to that of the
18-electron rule is satisfied. nido precursor. In each case, the metal fragment being added
Bonding within multiple stacks such as (20) and (21) is provides two electrons to cluster bonding. In equations (3) and
best dealt with in terms of the organometallic model, extended (4), the two electrons from the metal fragment replace those
to give electron counts for the stack as a whole. Triple-decker originally provided by the 2 charge. In equation (5), the
stacks (three ligands and two metal atoms) usually require monoanionic precursor loses H+ during the reaction.
30 electrons overall to give a stable diamagnetic complex,
although there is flexibility and between 26 and 34 electrons nido-[C2 B9 H11 ]2 + SmI2 (THF)x
can be accommodated. For an extra unit of the stack, 12 closo-Sm(THF)4 C2 B9 H11 + 2I (3)
more electrons should be added; thus, a tetradecker stack (four
nido-[C2 Me2 B9 ] 2
+ SnCl2 nido-SnC2 Me2 B9 H9 + 2Cl (4)
ligands and three metals) is stable with 42 electrons. Units
within the stacks are often derivatized Cp or [C2 B3 H5 ]2 nido-[C2 (SiMe3 )2 B4 H5 ] + SnCl2
ligands; both are sources of 6 electrons. THF
We now return to clusters with icosahedral cages. By
PSEPT, the 12-vertex closo icosahedral cluster requires 26 closo-Sn(THF)2 C2 (SiMe3 )B4 H4
bonding electrons. However, there are numerous examples in 100 C
which the number of electrons observed deviates from 26. In
closo-SnC2 (SiMe3 )2 B4 H4 (5)
CpFeC2 B9 H11 , the total electron count for cluster bonding
is 25. In [Fe(C2 B9 H11 )2 ] , it is not possible to allocate nido-[C2 Me2 B9 H9 ] 2
+ W(CR)Br(CO)4 R = 4-MeC6 H4
26 electrons to each half-cluster. For clusters with 24 26
electrons, an icosahedral cage is usually adopted despite
the apparent violation of PSEPT. An increased number of closo-[W(CR)(CO)2 (C2 Me2 B9 H9 )] (6)
electrons provides an explanation for the origin of the slip
distortion described earlier, for example, in [Au(C2 B9 H11 )2 ] The addition of a metal fragment to a nido-carbaborane
(23), each half-cluster has 27 electrons (for each half-cluster, anion may result in an increase in the number of cluster-
2 CH = 6 electrons, 9 BH = 18 electrons, Au contributes bonding electrons. For example, in equation (7), the reaction of
three electrons per cluster after six electrons have been nido-[C2 B8 H11 ] with RhCl(PMe3 )3 leads to the displacement
accommodated in nonbonding orbitals). of Cl and the combination of the carbaborane anion and
[Rh(PMe3 )3 ]+ fragments. The latter is a source of three
electrons (see equation 1) and hence the total cluster-electron
count increases by two during the reaction. Such an increase
will generate a change in skeletal geometry (see Section 3).
4 SYNTHESIS
Both [C2 B8 H11 ] and (PMe3 )3 RhC2 B8 H11 are nido clusters,
but each is based on a different deltahedral framework. An
Although, in this section, an attempt has been made to sys- alternative pathway might have been for (PMe3 )3 RhC2 B8 H11
tematize some synthetic routes to metallacarbaboranes,46,51 to extrude H2 or a PMe3 ligand, thus effectively reducing the
many other syntheses have been reported, which lack the electron count by two.
strategic quality that is desirable for efficient preparative
chemistry. nido-[C2 B8 H11 ] + RhCl(PMe3 )3
If a metallacarbaborane is represented as {MCB}, then nido-(PMe3 )3 RhC2 B8 H11 + Cl (7)
obvious methods of synthesis would be based on the
following combinations: (i) {M} + {CB}, (ii) {MB} + {C}, The reaction of nido-carbaborane anions with metal halides
(iii) {MC} + {B}, or (iv) aggregation of {M}, {C}, and is also a method of preparing commo-metallacarbaboranes
10 BORON: METALLACARBABORANES
a metal fragment into a nido cluster; the CpNi unit is a source (PPh3)CpCoC4Ph4 + 2BH3THF
of three electrons and one H atom is lost from the precursor in
Ph3BH3
order to retain an even electron count for the cluster.
H
4.4 Metallaborane with an Alkyne
B
An important method for the synthesis of carbaboranes is C C
C Co Co
the reaction of a borane cluster with an alkyne. However, an C
analogous reaction of a metallaborane cluster with an alkyne C C
C BH
is not commonly used to prepare metallacarbaborane clusters. C
C = CPh
Equation (21) illustrates one example.
B B B C
C
4.7 Construction of Stacked Complexes
Ru
Work directed at preparing and characterizing stacked com-
plexes has been developed since the late 1980s, and the synthe-
ses are carefully controlled.39,51 The principles of the approach
are outlined below, but may be summarized as an example of
the method. The archetypal sandwich compound is ferrocene, Scheme 2
12 BORON: METALLACARBABORANES
B = BH, C = CH AgOAc
B10H10
Hg Hg
H10B10 B10H10
Hg Hg
(34)
B10H10
4.8 Use of Lithiated Carbaboranes
(30)
The carbon-bound hydrogen atoms in closo-1,2-C2 B10 H12
(35) are acidic, and lithiation occurs readily (equation 23). Scheme 3
The monolithiated cluster disproportionates to a mixture of
1,2-C2 B10 H12 and 1,2-Li2 -1,2-C2 B10 H10 . Protection of one C
site can be achieved by using a t-BuMe2 Si group; the cluster The reaction of lithiated derivatives of 1,2-C2 B10 H12 with
can be deprotected with [n-Bu4 N]F. Lithiated derivatives are mercury(II) halides is a route to organomercury complexes
used to prepare a range of C-substituted derivatives.53 with Hg Ccarbaborane bonds.54 An interesting example is
shown in Scheme 3; 1,2-Li2 -1,2-C2 B10 H10 reacts with HgI2
H H H Li Li Li to give Li2 [Hg4 (C2 B10 H10 )I2 ]. When LiI is removed, a cyclic
C C C C C C tetrameric complex, which is described as a macrocyclic Lewis
BuLi + (23)
B10H10 B10H10 B10H10 acid, is produced.
C 4.9 commo-Clusters
The protected monosubstituted derivative 1-(t-BuMe2 Si)-1,2- 4.10 Clusters with More than 12 Vertices
C2 B10 H11 is the starting point for the synthesis of ligands
of type [H2 L]2 shown in Scheme 4. The length of the Although the chemistry of metallacarbaborane clusters
strap is critical if [H2 L]2 is to be a precursor to commo- with 12 vertices is extremely well established, that of
metallacarbaboranes of type [ML] . Scheme 4 illustrates a larger, single-cage compounds is a more recent development.
sequence used to link together two dicarbollide ligands via a Preparative routes to dicarbon metallacarbaboranes of the
C C link. Ligand [H2 L]2 interacts with a variety of first- platinum group metals having 11, 12, or 13 vertices have
row transition metal(III) ions (M3+ ), for example, Co3+ , Cr3+ , been reviewed.55 Metal capping of nido-[7,9-R2 C2 B10 H10 ]2
with concomitant deprotonation of the two nido cages to give is a general route to 13-vertex metallacarbaboranes. The nido
[ML] . The pyrazole-containing ligand present in complex precursor is produced by reduction of closo-1,2,-R2 C2 B10 H10 ,
(19) is synthesized from closo-C2 B9 H11 and [C3 H3 N2 ] . but this step always results in a separation of the carbon atoms
The development of preparative routes to ligands such as in the cluster cage (the carbons-apart product). Tethering
[H2 L]2 in Scheme 4 has been a breakthrough in the controlled the C2 unit to a C,C -bridging substituent allows the carbons
synthesis of the VFC group of commo complexes, which have adjacent product to be isolated (Scheme 5). The carbons-
potential biological uses (see Section 8). apart and carbons-adjacent species exhibit different redox
properties, with the dianion in Scheme 5 being further reduced
by Li metal to the corresponding tetraanionic arachno cluster.
By altering the length and flexibility of the organic bridge,
B
it is possible to gain control over the final positions of the
B B B B B two carbon atoms in the reduced product.56 A significant
B achievement has been the use of the carbon-tethered nido or
B B B B BuLi arachno clusters in reactions with RBCl2 to prepare the first
B B
Br(CH2)n Br
C B examples of 13- or 14-vertex carbaboranes, respectively.57,58
C B
B n = 3, 4, 5 Advances in the syntheses of metallacarbaboranes with 13
C B R vertices (MC2 B10 , MC4 B8 , M2 C2 B9 , M2 C3 B8 , M3 C3 B7 )
C B B
(CH2)n or 14 vertices (MC2 B11 , M2 C2 B10 , M2 C4 B8 ) have been
R
B B reviewed.56,59 Most recently, reduction of the carbon-tethered
R = protecting group R 1,2--(CH2 )3 -1,2-closo-C2 B11 H11 by Na and subsequent
B = BH C B reaction of the reduced, open cage with [(p-cymene)RuCl2 ]2
C = CH (or CR as shown) C B
B has given rise to the isomeric, 15-vertex clusters (36) and
(37).60
B
B B B B
Deprotection
L L
B
Ru Ru
B B 2
B B B B
B C B C
B B B B B C B B
B B B B
B B
B B B B
B B B C
B B B B B B
C B C B
C B C B
B B
H B = BH B = BH
B
(CH2)n KOH, EtOH
(CH2)n L = p-cymene L = p-cymene
B H (36) (37)
C B C B
C B C B
B B
B B 5 SKELETAL ISOMERISM
B B B B B B B B
B B
Of the polyhedra in Figure 1, only the octahedron and
[H2L]2 icosahedron possess equivalent vertices. closo-[B12 H12 ]2
contains only one B environment and the introduction of
one C atom in place of B generates [CB11 H12 ] for which
Scheme 4 there is only one structure. Introduction of two C atoms to
14 BORON: METALLACARBABORANES
2
B
B B
C B B B Excess Na C B
B THF
C B
B B
C B B B
B B B B
B B
B = BH
Scheme 5
give C2 B10 H12 leads to three possible isomers: 1,2-, 1,7-, and symmetry. However, these are guidelines, not rules. In (5), for
1,12-C2 B10 H12 (equation 24). example, all four guidelines are met: the Ru atom occupies
the unique site of the octadecahedron with connectivity six,
H H C while the two C atoms are mutually apart (a carbons-apart
H H isomer) and are in sites of connectivity four.
B B B B B C
B B Examples of thermal skeletal isomerization are as
C2 H2 B
follows. The 11-electron pair cluster closo-Cp2 CoNiCB7 H8
B B
B (Scheme 6) has a structure based upon a bicapped square
B B B B antiprism (Figure 1). This polyhedron has two distinct types
B B B
of vertex: (i) two apical sites each of which has a connectivity
B
B of four within the cage and (ii) eight equatorial or square
B = BH B = BH, C = CH antiprism sites each of which has a connectivity of five within
B10H14 1,2-C2B10H12
(24) Ni B
470 C
B B
B B Ni Co
B B
C C 300 C
B B
B B B B B B B B
B B B B Co B
B B
700 C
B B C C
B B B C
B B B B
Ni
C B 450 C
1,12-C2B10H12 1,7-C2B10H12 B
B Co
B
Introducing a metal atom into the carbaborane framework Minor
B
increases the number of possible isomers. In the synthesis of B B
B
a metallacarbaborane, the kinetic product may not necessarily
Major
be the thermodynamically preferred isomer, for example,
C B
in the synthesis of CpCoC4 Ph4 BH, the first isomer to be
formed rearranges spontaneously to the thermodynamically
favored one (Scheme 1). An understanding of the mechanisms 450 C
B
B Co
Ni
for polyhedral rearrangements among metallacarbaboranes
remains relatively undeveloped, but proposals usually B
B B
involve nondissociative processes. General preferences follow B
the guidelines that (i) carbon atoms prefer sites of low B = BH, C = CH
Co = CpCo
connectivity, (ii) carbon atoms tend to be apart from one C
Ni = CpNi
another (but see Section 4.10), (iii) metal atoms show a
tendency for sites of relatively high connectivity, and (iv) a
metallacarbaborane cluster tends to exhibit some degree of Scheme 6
BORON: METALLACARBABORANES 15
Cl Scheme 8
B
C B Br
C
Electrochemical data for a wide range of metallacarbab-
Co
orane clusters have been collected together in several
reviews.6870 For metallacarbaboranes containing transition
metal atoms, the measured redox couple is usually assigned
to the process Mn+ + e M(n1)+ . However, this may be
a formal designation since the bonding in a metallacarbabo-
250 C rane cluster is delocalized. Some general conclusions68 are as
Cl Br
follows: (i) if the carbon atoms are adjacent to the transition
metal atom, the reduction process for the cluster occurs more
B B easily than when the carbon atoms are more remote from
Cl Cl
the metal atom; (ii) metallacarbaborane clusters containing
B B an MC2 B10 H12 core exhibit lower reduction potentials than
C C C C
B B clusters with an MC2 B9 H11 core for a common metal, M; and
Br Cl (iii) when more than one metal is present in a metallacarbab-
Co Co orane cluster core, the metals influence one another.
Electrochemical studies of sandwich complexes have
also included multiple stacked systems.5,7,68 In triple-decker
complexes such as (20), a series of diffusion-controlled
Scheme 7 reversible one-electron redox processes is observed. Thus,
for (20) (CMe replaced by CEt), the processes are
the cage. After thermolysis, the metal atoms end up in the sites summarized in Scheme 8 in which [Co Co] represents
of higher connectivity and the carbon atom remains in a site the core of the triple-decker sandwich complex. It is
of low connectivity.61 the metal atoms (not the sandwich layers) that are the
When 1-(CpCo)-2,3,-C2 B9 H11 is heated between 400 centers for the redox changes; however, the reduced
and 700 C, six isomers are obtained in which the or oxidized species are stabilized by the ability of the
carbon atoms have migrated around the cage positions.62 multiple-sandwich structure to delocalize electronic charge.
Thermal rearrangements of (CpCo)2 C2 Bn Hn+2 (n = 6 8) Detailed studies of (4-MeC6 H4 CHMe2 )Ru(Et2 C2 B3 H3 )Ru(4-
lead to isomeric products,63 and an exo nido closo MeC6 H4 CHMe2 ) (Ru Ru) and CpCo(Et2 C2 B3 H3 )Ru(4-
skeletal rearrangement is observed when exo nido-5,6,10- MeC6 H4 CHMe2 ) (Co Ru) by voltammetric, coulometric,
(Cl(PPh3 )2 Ru)-5,6,10-(-H)3 -10-H-7,8-C2 B9 H8 is heated in electron paramagnetic resonance (EPR) spectroscopic, and
benzene under reflux conditions.64,65 In the rearrangement optical spectroelectrochemical methods have been used to
of icosahedral [3,1,2-(CO)2 (C3 H5 )Mo(PhC2 B9 H11 )] to the illustrate that there is complete delocalization of charge in the
carbons-apart isomer [3,1,9-(CO)2 (C3 H5 )Mo(PhC2 B9 H11 )] , cations (Ru Ru)+ and (Co Ru)+ . This is encouraging for the
a nonicosahedral intermediate has been isolated; the application of the stacked complexes in the construction of
rearrangement is facile, occurring at room temperature, electroactive polymers.71 A redox series involving a linked
apparently to relieve steric crowding.66 A final example stack with iron centers is shown in Scheme 9. Related
involves the little-studied six-membered closo-MC2 B3 cage. studies with Co- and Fe-containing systems have been
When heated to 250 C, closo-1,2,3-Cp Co(Et2 C2 B3 -4,6-Cl2 - reported.72,73 The alkyne-coupled clusters in (22) exhibit
5-Br) rearranges as shown in Scheme 7, while heating double one-electron reductions followed by a single two-
closo-1,2,3-Cp Co(Et2 C2 B3 Br3 ) leads to a single carbons- electron reduction. These results are interpreted in terms of
apart isomer.67 significant electronic communication between the four metal
centers.42
6 ELECTROCHEMISTRY
7 REACTIVITY
The discussion of the electrochemical properties of
metallacarbaboranes involves the compounds that are best It is extremely difficult to generalize about the reactivity
subdivided into clusters and stacked complexes. patterns of metallacarbaborane clusters. Some properties are
16 BORON: METALLACARBABORANES
FeIII
O O
FeIII
O O
B
B C C B Yb
B
B B B C
C
Scheme 9
B
B B
B B
outlined below, but the reader is directed to the literature for
details of the reactions of specific compounds.46,1217 B
B = BH, C = CH
(38)
7.1 Metal Exchange Reactions
Gas phase
closo-1-Sn-2,3-C2 Me2 B4 H4 + CpCo(CO)2 7.3 C and B Derivatization
closo-CpCoC2 Me2 B4 H4 + closo-CpCoSnC2 Me2 B4 H4 (25)
For C-derivatized metallacarbaborane clusters, the sub-
stituents attached to the cage carbon atoms are usually
7.2 Ligand Substitution at the Metal Atom introduced into the carbaborane precursor. Examples have
been given earlier in equations (4), (5), (8), and (12), and
For transition metal containing metallacarbaboranes, Scheme 4.
reactions at the metal center with no concomitant change Electrophilic substitution reactions are used to introduce
to the cluster core are possible. The simplest type of reaction B substituents into metallacarbaboranes. For example, the
is ligand substitution. In equation (26), the three carbonyl electrophilic bromination of 1-(CpCo)-2,3-C2 B8 H10 gives
ligands (each a two-electron donor) are replaced by a - a mixture of 10-Br-1-(CpCo)-2,3-C2 B8 H9 and 4-Br-1-
bonded benzene ring (a six-electron donor). When the net (CpCo)-2,3-C2 B8 H9 . In the presence of AlCl3 and at
BORON: METALLACARBABORANES 17
is catalytically active. Cl H
Ph3P PPh3
H H Ru
Ph3P PPh3 B B B
H B C C B C
Rh PPh3
H H B C
B B B C B B B C
C C Rh Ph3P + B B
H B B B B
Ru
PPh3 (28) Ph3P B B B B
B B
B B B B H H
B B B B
Cl B B
B B B = BH, C = CH, B = B B = BH, C = CH
closo exo nido (41) (42)
B = BH, C = CH, B = B
The exo nido and closo cage ruthenium clusters have been tested using cyclohexene, 1-methylcyclohexene,
RuCl(PPh3 )2 (C2 R2 B9 H10 ) (R = H or Me) (41) and (42), and 2,3-dimethylbut-2-ene for their catalytic activity (under
respectively, exhibit a high activity as cyclopropanation ambient conditions) in internal alkene hydrogenation.86
catalysts, for example, in the reaction between ethyl diazoac- Further examples of metallacarbaborane catalytic activ-
etate and alkenes (equation 29). During cyclopropanation, an ity have been reviewed by Grimes.43 The complex
exo nido closo rearrangement should occur. [(7-PPh2 -8- (Ph3 P)2 Ir(H)2 (closo-CB11 H6 Br6 ) catalyzes the hydrogenation
R-7,8-C2 B9 H10 )Rh(PPh3 )2 ] (R = H, Me) and [(7-PPh2 -8-Me- of cyclohexane and can be recycled up to five times without
7,8-C2 B9 H10 )Rh(cod)] are also active in the cyclopropanation decomposition; related results for ethene are summarized in
of alkenes with diazoacetates.84 Scheme 10.87 The effects of the halogen substituent and of the
steric demands of the phosphine have been detailed.88
R H Group 4 metallocenes with constrained geometries are
highly active catalysts. The replacement of one or two
CO2Et
[C5 R5 ] ligands by nido-[C2 B9 H11 ]2 ligands (see (3)) gives
[Ru]
R + N2CHCO2Et
(29) a means of modifying metallocene catalysts.89,90 Examples
R CO2Et include (43), which is proposed as the active catalytic
H
species in the hydrogenation of internal alkynes to (Z)-
alkenes.91 Complex (44) incorporates a nido-C2 B4 cage and
this complex catalyzes the polymerization of ethene to high
Silver phosphines in association with [1-closo-CB11 H12 ] molecular weight polymers under ambient conditions.92 The
and [1-closo-CB11 H6 Br6 ] are highly active Lewis acid cata- catalytic activity of single-walled carbon nanotube-supported
lysts for some hetero-Diels Alder reactions. Very low catalyst nickellacarbaboranes has also been explored.93
loadings are required (0.1 mol%) and turnover frequencies of The application of metallacarbaborane clusters as
4000 h1 are observed.85 The complexes [(PPh3 )2 Rh(nbd)] radiometal carriers for radioimmunodiagnosis and radioim-
[closo-CB11 H12 ] and [(PPh3 )2 Rh(nbd)][closo-CB11 H6 Br6 ] munotherapy has been explored, with VFCs (see Sections
C H2C CH2
C
B B B B
B B B B
B
B
Br PPh3
B PPh3 Br
Br B B Br B
B B H Ir Br B B
B B Br
Ir
Br Br
B H PPh3 Br Br
PPh3 B
Br
Br
B = BH, C = CH
C2H6
Scheme 10
BORON: METALLACARBABORANES 19
B B
B B B B
B B B B B
B B B
B B
B Me
B EtC C
C Et B
Ti Me O O B C
HN B C
B C Me2P
Hf H PMe2 N N M
N N C
HO B C
B B
O
O
B B
B = BH; C = CH B = BH B B B
NH
(43) (44) O
HO P O B
N O
O O
2.2 and 4.9) being central to these studies.36,94,95 It is necessary
to provide a radiometal-containing system (the metallacarbab-
orane) that is suitably functionalized to enable conjugation HO
B = BH, C = CH
to monoclonal antibodies. The dicarbollide ligand present M = Fe or Co
in complex (19) can encapsulate a radiometal atom (e.g., (45)
57
Co) to form a particularly stable metallacarbaborane commo
cluster. The first examples of direct labelling of proteins
with 121 At using a nido-carbaborane, a VFC, or closo- The ability of [3,3 -M(1,2-C2 B9 H11 )2 ] (M3+ = Co3+ ,
decaborate(2-) clusters were reported in 2007.96 Salts of Fe , Ni3+ ) to act as Cs+ sensors in ion selective electrodes
3+
[1-CpFe-2-Me-2,3,4-C3 B7 H9 ]+ and the complex 1-CpFe-2- has been assessed. The related complexes [3,3 -Co(1-Me-
Me-2,3,4-C3 B7 H9 have been found to be effective cytotoxic 2-(CH2 )n OR-1,2-C2 B9 H9 )2 ] (n = 3, R = Et; n = 3, R =
agents against human and murine tumor cell lines; the (CH2 )2 OMe; n = 3, R = (CH2 )3 Me; n = 6, R = (CH2 )3 Me)
agents act by inhibiting the de novo purine synthesis of and [3,3 -Co(1-Ph-1,2-C2 B9 H10 )2 ] and [3,3 -Co(1,7-Ph2 -
L-1210 cells, thus reducing DNA and RNA syntheses.97 1,7-C2 B9 H9 )2 ] act efficiently in 137 Cs, 90 Sr, and 152 Eu
1-Cp-1-Br-2-Ph-1,2,3,4-VC3 B7 H9 and commo-Nb-1-Cl-(4- extraction.105,106
Me-1,2,3,4-NbC3 B7 H9 )2 are also cytotoxic agents; the One challenge within the area of conducting electroactive
vanadium-containing complex exhibits significant activity polymers such as polypyrrole (PPy) is increasing the stability
against the growth of cultured human solid tumors.98 The tan- of the materials. By doping PPy with [Co(C2 B9 H11 )2 ] ,
talum and niobium-containing species CpTaCl2 (Et2 C2 B4 H4 ), the material becomes more resistant to overoxidation by
CpNbCl2 (Et2 C2 B4 H4 ), Cp TaCl2 (Et2 C2 B4 H4 ), CpTaCl2 300 500 mV.107
{(Me3 Si)2 C2 B4 H4 }, and CpTaCl2 (Me2 C2 B4 H4 ) are active
against suspended tumors, and result in cell death in a
number of tissue culture lines including murine L1210 lym-
phoid leukemia.99 Metallacarbaborane-containing nucleoside 9 FUTURE WAYS FORWARD
conjugates with thymidine, 2 -O-deoxyadenosine, 2 -O-
deoxyguanine, or 2 -O-deoxycytidine100,101 provide building In addition to the areas already discussed in this article
blocks for the synthesis of, for example, iron(III) and and, in particular, development of applications in biological,
cobalt(III)-containing dinucleotides (45). The synthetic path- medicinal, and materials chemistry, several aspects are of
way to (45) generates a series of synthons for the preparation of current research interest. Section 4.10 introduced the steadily
bioinorganic DNA/metallacarbaborane conjugates.102 Related expanding area of single-cage metallacarbaborane clusters
mononucleotide conjugates may function as electrochemical with more than 12 vertices. The role of carbaboranes and
tags, and are proposed as labels for electrochemical coding of metallacarbaboranes within supramolecular chemistry108 has
DNA.103 been actively investigated in the last decade. One of the best-
Technetium and rhenium coordination chemistry associ- explored areas is that of multicluster mercuracarbaboranes,
ated with the introduction of 99m Tc into radiotherapy and which act as macrocyclic Lewis acidic hosts for electron-rich
radioimaging agents is of active current interest, and the (anionic or neutral) guests.54
application of nido-carbaborane ligands has recently been Finally, small metallacarbaboranes containing the C2 B4
explored. Microwave heating assists the formation of rhenium unit have been the subject of much study in the last few
5 -carbaborane complexes in aqueous solution, and similar decades. However, Hosmane has made a pertinent point: the
conditions are effective at the tracer level for the preparation area has depended on supplies of B5 H9 from government
of 99m Tc complexes.104 surplus, which are no longer available.109
20 BORON: METALLACARBABORANES
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BoronNitrogen R3CCR 3
Alkane
R 3B :NR3
Amineborane
R2C=CR2
Alkene
R 2B=NR2
Aminoborane
Compounds RCCR
Alkyne
RBNR (R 2CCR 2)3
Iminoborane Cyclohexane
(R2BNR2)3
Cycloborazane
(RC=CR)3 (RB=NR)3
Based in part on the article Boron Nitrogen Compounds by Robert Benzene Borazine
T. Paine which appeared in the Encyclopedia of Inorganic Chemistry, R R R R
First Edition.
C N C B
R 2C + CR 2 R2B BR2 R 2C CR2 R2N NR2
Allyl cation Diborylamine Allyl anion Diaminoborane
1 Introduction 1
2 Amine-boranes 1 R2C=C=CR2 R2C=B=NR2 R2N C C R2N B NR
3 Aminoboranes 3 Allene Alkylideno- Aminoalkyne Amino-
4 Iminoboranes 7 aminoborane iminoborane
5 Other Low-coordinate Conditions 9
6 Pseudohaloboranes 9
Figure 1 Some known isoelectrical/isostructural compound pairs
7 Cationic Species 10
8 Borazines 11
9 Pyrazaboles 11 a selection of work that illustrates recent advances in each
10 Polypyrazolylborate Coordination Chemistry 12 subfield has been presented. However, recent reviews were
11 Additional Ring Systems 12 sought for each of the sections listed in the table of contents.
12 Boron Nitride 13
13 Related Articles 14
14 References 14
2 AMINE-BORANES
starting from the gas-phase value, the BN bond distance diazabicyclo[2.2.1]hept-2-ene and 2,3-diazabicyclo[2.2.2]oct-
decreases with increasing solvent polarity (1.62 A in hexane 2-ene have now been isolated,13,14 and in most other cases
and 1.57 A in water). This suggests that the short BN distance the azo-borane complex is stable in the presence of alkenic
found in the solid-state structure may arise from crystal unsaturation. The Lewis acidity of methylene boranes has
medium effects. Calculations of 11 B NMR shifts (IGLO) also been recognized for some time, and satisfaction of the electron
suggest that variations in 11 B delta data with solvent may deficiency in these species has been considered to occur by
be less a result of solvent effects on nuclear shielding and nonclassical (5) and classical (6) intramolecular interactions.
more a result of structural changes induced in the molecule by It has now been reported that intermolecular Lewis acid-base
the medium. complexes (7) of these unique species can also be formed.15
The thermal decomposition of H3 BNH3 has been studied The strong Lewis acid (CF3 )3 B can only be isolated with a base
by 11 B NMR in aprotic solvents at temperatures above such as ammonia. While the BN bonds are extremely strong,
80 C.8 Three reaction types were found. In etheral solvents, the NH groups undergo a wide range of interesting reactions.
decomposition occurred by hydrogen loss with formation For example, (CF3 )3 BNH3 forms Cs[(CF3 )3 BNX2 ] (X=Cl,
of cycloborazanes and eventually borazine, (HBNH)3 . Br), when combined with the appropriate cesium hypohalite.16
In pyridine solution, base displacement took place with
generation of pyridineBH3 ; in acetonitrile solution, hydrogen
loss and solvent hydrogenation or hydroboration occurred. t-Bu
These results suggest that it may not be possible to study the
reaction chemistry of the monomeric aminoborane H2 BNH2
N
in solution prior to its undergoing condensation reactions. A R
triarylborane with orthohydrogen bonding groups was shown B
to strangely bind ammonia through all four of its atoms.9 R Ar
This was a rare example of a host-guest system10 able to (7)
recognize ammonia.
The reactivity of BX3 fragments toward bifunctional
Lewis bases (e.g. R2 ENR2 , RE(NR2 )2 , and E(NR2 )3 ; E=P,
As) are also of fundamental interest.11 It is clear that a
combination of substituent inductive effects, E... N p d O O
electronic effects, as well as steric influences are responsible amine BH2X
BL2
for the BX3 coordination site selectivity and selected bond- (9)
breaking chemistry found in these complexes. The mechanism O O X = CONHR, CO2H, CO2R,C(OR) NR
for hydrolytic decomposition of amine-borane complexes also O
n
continues to be of interest. A comparison of the hydrolysis of
(8)
benzylamine-borane with the hydrolysis of various arylamine-
boranes has been reported,12 and the results are important for
the selection of borane adducts as practical hydridic reagents
Several amine-borane complexes have recently been
in aqueous phase reductions.
reported that have potential applications. For example,
Although tertiary amine-borane and aromatic amine-borane
borylated crown ethers (8) provide a host-guest envi-
complexes are common, azo-boranes (1) and (2) were
ronment for molecular recognition of primary amines.17
unknown until recently. Borane complexes (3) and (4) of 2,3-
There is also interest in the synthesis and study of
pharmacological properties of boron analogs of isoelec-
BH3 BH3 tronic/isosteric biologically important molecules. These
BH3
N N include selected amino acid analogs (9) (11) and boronated
R N BH3 nucleosides and nucleotides (12) and (13).1823 Studies
N N
(5) (6)
BORON NITROGEN COMPOUNDS 3
OH OH SnMe3 BCl2
2Me3SnCl
(12) (13) Cl3nMenSi N + 2BCl3 Cl3nMenSi N
SnMe3 BCl2
(4)
3 AMINOBORANES
SnMe3 SnMe3
Me3SnX
R N + R2BX R N (5)
Aminoboranes have the general formula R2 B... NR2 , and SnMe3 BR2
they are the isoelectronic analog of alkenes. The boron X = Cl, Br
and nitrogen atoms are formally three-coordinate, and the SnMe3 SnMe3
electron deficient and coordinatively unsaturated boron atom Me3Si N + X2BCl Me3Si N (6)
in monomeric molecules is stabilized by sterically bulky SnMe3 BX2
groups and by electron donation from the amido group. When
SnMe3
these steric and electronic influences do not provide sufficient Me3SnCl
Me3Si N (Me3SiN BCl)3 (7)
stabilization for the boron atom, the fragment typically
BCl2
forms cyclic aminoboranes, for example, (R2 BNR2 )2 and
(R2 BNR2 )3 . The factors influencing this chemistry have been
systematically studied. Extensive reviews of aminoborane The related reaction chemistry of the B-silylaminoborazine
chemistry appeared in 1970,26 1980,27 and in 1991 Noth [(Me3 Si)2 NBNH]3 with HCl has been examined as a
briefly summarized some recent work from his group.28 Recent means to produce condensed polyborazine materials.32 The
emphasis on these molecules has centered on the development reaction of BCl3 and (Me3 Si)3 N at 23 C gives the expected
of precursors for formation of low-coordinate fragments, aminochloroborane (equation 8), but in surprisingly low yield;
for example, amino-iminoboranes, R2 NB=NR, and amino- at higher temperatures, methylation of the boron center occurs
(equation 9). This result points out the potential limitations of
phosphanylidene boranes, R2 N... B=PR. The subfield of
this chemistry. In related studies directed at developing boron
amino-iminoboranes will be discussed in Section 4, while
nitride precursors, Paciorek33 examined routes to several
selected advances in other aspects of aminoborane chemistry
silylaminoborane open-chain compounds through Me3 SiCl
are discussed here.
elimination reactions (equations 10 and 11).
Historically, aminoboranes have typically been prepared
by XY elimination reactions between borane BX3 and amine
(Me3 Si)3 N + BCl3 (Me3 Si)2 NBCl2 (8)
NY3 reagents (equation 2) and by salt elimination reactions
(equation 3). Dehydrocoupling catalyzed by rhodium has (Me3 Si)3 N + BCl3 MeBCl2 + N(SiMe2 Cl)x (SiMe3 )3x (9)
recently been discovered as a convenient, clean route
to aminoboranes.2931 Many seemingly straightforward (Me3Si)2NBCl2 + (Me3Si)2NB(NH2)N(H)SiMe3
elimination reactions of haloboranes with NH3 and primary
and secondary amines have been examined.27 In many
cases, oligomeric products are obtained, and in some cases
N(SiMe3)2 N(SiMe3)2
the desired aminoborane products are difficult to separate
B B
from organoammonium salt by-products. In other cases, Me3SiHN N
H NH
the expected amino substitutions could not be achieved in
good yields owing to sluggish elimination reaction kinetics. B
Me3SiHN N(SiMe3)2
As a result, a significant effort has been given to the (10)
development of silane and stannane elimination pathways
3(Me3 Si)2 NB(NH2 )NH(SiMe3 ) + BCl3 NEt3
by utilizing silylamine and stannylamine reagents.28 For
example, stannazane cleavage of Cl3n Men SiN(SnMe3 )2 with B[N(H)B[N(SiMe3 )2 ][N(H)SiMe3 ]] (11)
excess BCl3 gives bis(dichloroboryl)silylamines (equation 4),
while reactions of equimolar amounts of RN(SnMe3 )2 Several novel, new aminoboranes with electronically
and Me3 SiN(SnMe3 )2 with various boron halides give or sterically demanding substituents have been reported.
4 BORON NITROGEN COMPOUNDS
(17) (18)
F3C
B N
N(i-Pr)2
F3C
B
(14) BN = 1.37 B
(i-Pr)2N
The tris(trimethylsilyl)methyl, (Me3 Si)3 C, substituent is a
sterically bulky group, and can be used in the formation of (19)
low-coordination number environments at boron. Eaborn35
has reported the synthesis of the diaminoborane (15) from B6 (NMe2 )6 (18). Paetzold39 has subsequently discussed the
aminolysis of (Me3 Si)3 CBCl2 . This compound is unusual occurrence of subvalent group 13 species, and it is
since most other bis(amino)boranes without organic groups clear that transient carbenoid R2 NB species should have
on nitrogen readily undergo decomposition with loss of considerable reactivity toward various unsaturated organic
ammonia and ring or oligomer formation. Compounds of fragments. Meller40 has exploited this theme to prepare several
comparable stability include HB(NH2 )2 , which is stable subvalent boron species, and much of that work has been
in the gas phase or in liquid NH3 but decomposes with briefly reviewed.40 For example, the tetrahydroborolo[3.2-b]
NH3 loss in the liquid state, and B(NHAr*)(NH2 )2 , which borane (19) and triborabicyclo[3.3.1]nona-3,6-diene (20) were
is thermally stable. Compound (15) can be sublimed obtained in reaction with benzene. That care must be exercised
in vacuo at 80 C, but sublimation is accompanied by over the generality of these systems is illustrated by the fact
formation of (16) (equation 12). This compound is the that Na/K reduction of F2 BN(Me)(i-Pr2 C6 H3 ) in DME gave
first example of a bis(aminoboryl)amine without N- a complex mixture of products including some that contained
organyl substituents. Known analogs with N-alkyl or -aryl methoxylated borane fragments. Finally, in a related system,
substituents typically decompose with formation of cyclic the combination of PbCl4 with Li2 PhB(N-t-Bu)2 gave a 1,3-
products.36 diaza-2-plumba-4-boracyclobutane (21).
H SiMe3
Me3Si SiMe3 N(i-Pr)2
NH2 H2N N
B B
Me3Si B SiMe3 B
NH3 (12) (i-Pr)2N t-Bu t-Bu Ph
Me3Si NH2 NH2
Me3Si SiMe3 B N(i-Pr)2 N Pb N B
SiMe3 B
B N Pb N
(15) (16) Ph t-Bu
t-Bu
The fluorenyl fragment should also provide considerable
(20) (21)
steric protection, and to this end, bis(fluorenyl)aminoboranes
(17) have been prepared by reaction of R2 NBCl2 with fluorene
deprotonated by potassium or by combination of R2 NBCl2 It was noted that the bis(fluorenyl)aminoboranes (17) are
(R=Et, i-Pr, i-Bu, s-Bu) with LiC13 H9 .37 This result contrasts relatively stable compounds. The corresponding monofluo-
in its outcome in an important way with related reductions renyl aminohaloboranes (22) can also be prepared, and they
involving R2 NBCl2 . For example, it has been observed that serve as a source of the alkylidenylaminoborane (23).41,42
reduction of (Me2 N)2 BCl with Na/K alloy leads to a series of The compound (23) was the first of a family of alkylideno
acyclic Bn(NMe2 )n+2 (n = 2 5) compounds containing BB aminoboranes, R2 N=B=CR2 that can be considered to be
bonds. Noth28 and Baudler38 further observed the formation allene or aminoalkyne analogs. These compounds, containing
of several cyclic and cage subvalent BI compounds including two-coordinate boron, are kinetically stabilized by sterically
BORON NITROGEN COMPOUNDS 5
X
N B H
MNR2 TiCl 4
N B N B B TiCl 3
HNR2
MX N
(23)
Fe2(CO)9
(22) X = Cl, Br (23)
(OC)4Fe
demanding substituents R and R and by electron donation Fe2(CO)5 B
from the amino group to the coordinatively unsaturated boron N
center. The tmp (t-Bu)2 N, and (t-Bu)(Me3 Si)N groups serve
well in this role; however, the (Me3 Si)2 N group does not.
In the last case, the incipient (Me3 Si)2 N=B=fluorenyl com-
pound spontaneously dimerizes. Despite kinetic stabilization,
(OC)3Fe
the B=C bond in the fluorenyl aminoboranes is highly reac- L(CO)3Fe
tive (Scheme 1) toward polar addition reactions as well as L
B B
[2 + 2] and [2 + 3] cycloadditions.4143 In addition, transi- N N
tion metal reagents TiCl4 , Fe2 (CO)9 , Fe(CO)5 , CpCo(CO)2 ,
CpMn(CO)3 , and (C6 H6 )Cr(CO)3 have been observed to react
with (23) (Scheme 2).4446
The reactivity of two related alkylideno aminoboranes, i-
Scheme 2
Pr2 N=B=C(SiMe3 )2 47,48 and tmp=B=C(SiMe3 )2 ,48 has been
extensively studied. The chemistry displayed is similar to that
depicted in Scheme 1, and additional reaction patterns are
summarized in Scheme 3. R
N B P
Cr(CO)5
H
X PH2 P
R2N B (27)
R2N B R2N B B NR2
PH2 PH2 P
H phosphorus atom carries H, SiMe3 , or organyl fragments.49
(24) (25) (26) This includes the formation of boryl phosphanes (24),
boryl bis(phosphanes) (25), diazadiphosphetidines (26), cage
species,50 and the first stabilized phosphanylidene borane
Aminoborane fragments R2 NB have recently been reported fragment (27) having a formal P=B double bond.51 Some
to stabilize a variety of phosphanyl species where the of the reaction chemistry of one phosphanylborane is
summarized in Scheme 4.
R Finally, several years ago, Richman52 reported the for-
mation of a boron inclusion compound (28) that alter-
X RN3 N
HX R natively could be considered to be a tris(amino)borane.
N B tmpB CR2 B
N2 N Practical applications have been found for several aminob-
R R
oranes. For example, an aminoborane reagent (29) has been
R H reported to be useful in enantioselective addition of allyl to
RRC O
aldehydes.53
O R R R Ph Ph
N B N B O +
R N N
R R B
R R N N
TolO 2S B SO2Tol
3 N
(i-Pr)2N SiMe3
B SiMe3
Br Br
Me
SiMe3 (i-Pr)2N Si Me
(i-Pr)2N
B SiMe3 Br2 B SiMe3
Me H
(1) MeLi Me H
(2) HCl
500_600 C
SiMe3 C3H6
(i-Pr)2N B
RBBr2 SiMe3
Me3SiN3
(i-Pr)2N SiMe3
B SiMe3 (i-Pr)2N
SiMe3
Br B Br HC(O)NMe2
B
Me
t-BuN C (Me3Si)2N N2
Scheme 3
SiMe3
P(SiMe3)2
P(SiMe3)3 P
(i-Pr)2N B
(i-Pr)2N B B N(i-Pr)2
P(SiMe3)2 P
SiMe3
LiP(SiMe3)2 NH2
Cl
LiCl B
(i-Pr)2N B
(i-Pr)2N P(SiMe3)2
P(SiMe3)2
(OC)5W
2 NH3
W(CO)5 NMe2
NMe3 NH4Cl
Cl
(i-Pr)2N B
Cr(CO)5 NMe2 P(SiMe3)2
NMe3
Cl 0.5 i-Pr2NBCl2
Me3SiCl
B
(i-Pr)2N P(SiMe3)2
Me3SiN3
Cr(CO)5 Me3SiCl
P
Scheme 4
BORON NITROGEN COMPOUNDS 7
B N
N B O
Br O
B N N B R
Br H
Br2
RCO2H
Cp2NbH B(All)3
B N
B N
B N B(All)2
H Nb Cp
Cp R2BCl
Cp2Ti CH2 Me3SiCl
OC(CF3)2
B N B N
H Ti Cp N B
B N R
H Cp
O CF3
CF3
Scheme 5
8 BORON NITROGEN COMPOUNDS
t-Bu t-Bu
N B
t-Bu B N t-Bu t-Bu t-Bu
Si Si B N
Me Me Si
Me Me Mes Mes
SiMe2 SiMes2
t-Bu
t-Bu B N t-Bu N
(30) Me2Si Sn
N
2 SiMe2 t-Bu
t-Bu t-Bu
Sn[N(SiMe3)2]2 B N
t-Bu t-Bu
B N t-Bu N Sn
Si N
Me Si Si Me t-Bu Me
Me t-Bu
Me Me B N
(Me3Si)2N Sn-N(SiMe3)2
Scheme 6
at the boron atom across a SnN bond.59 The reaction of borylated lactam,61 and phosphonic and phosphinic acids
acetamide with (31) gives an O,N-diborylated acetimidic produce O-borylated phosphonates and phosphinates.62 These
acid, while N-methylacetamide leads to N-borylated N- reactions may in fact find some use in organic synthesis.
methylacetamide.60 Pyrrolidone reacts with (30) to form a Finally, Noth and coworkers63 have explored the reactions
tmp
N
O N t-Bu N
tmpB H tmpB O
N t-Bu N t-Bu
H H
NH
MeCONH2
R O
N O
tmpB
N t-Bu R R
H H2 N H
MeCONHR
or tmpB N t-Bu N
(31) tmpB
NR
O N t-Bu
tmpB R2P(O)OH H
N t-Bu
H t-Bu
O H
O P R N H H
B
tmpB R H B B
B H
N t-Bu N H
H tmp H
(32)
Scheme 7
BORON NITROGEN COMPOUNDS 9
of (31) with B5 H9 , B3 H7 THF, and B10 H14 . Pentaborane(9) with R=Ph, R =Me shows that the interaction is localized
is unreactive, but B3 H7 THF hydroborates the BN bond, between the B...
NMe2 groups, the B...B bond is long, and the
giving (32). More recently, it was shown that (31) combines N-B-B planes are twisted out of coplanarity by approximately
with ECl3 (E=Ga, In) to yield tmp=B=N(ECl3 )t-Bu.64 60 degrees. Subsequent reduction of this species produces
Combination of t-BuBN-t-Bu amd Cp2 M(H)Cl (M=Zr, Hf ) a dianion [Ph(Me2 N)B... B(NMe2 )Ph]2 . Its structure shows
leads to the compounds {t-BuB(H)=N(t-Bu)}MCp2 Cl where that the B2 N2 array is planar and the BB bond is shortened,
the iminoborane appears to be bound side-on in a manner but this occurs at the expense of B=N overlap, as evidenced
analogous to alkynes.65 by elongation of the BN bond distances. This is consistent
with the valence bond representation shown in equation (13).
2
5 OTHER LOW-COORDINATE CONDITIONS Ph NMe2 Ph NMe2
2e
B B B B (13)
Me2N Me2N
Compounds with B... N units in open-chain molecules, Ph Ph
R = Br, Me 6 PSEUDOHALOBORANES
NMe2 NMe2
Fe2(CO)9
B (OC)4Fe B
dark As described by Paetzold,1,72 azidoboranes have played
R R an important role in the synthesis of iminoboranes and vari-
(33)
ous boron nitrogen heterocycles discussed elsewhere in this
Fe2(CO)9 hn
article. As a result, there is continuing interest in these reac-
dark tive reagents. Neilson73 has reported the synthesis of the
R = t-Bu R stable azidoborane (Me3 Si)2 N(t-Bu)BN3 by treatment of a
B chloroborane precursor with Me3 SiN3 . This reagent was then
NMe2 used to oxidize (silylamino)phosphines by the Staudinger
Fe reaction (equation 14) to (borylimino)phosphoranes (39). Sim-
(CO)3
ilar chemistry is found for three-coordinate aminophosphines
(equation 15). It is interesting to note that the two-coordinate
Scheme 8 methylene- and iminophosphines also undergo oxidation to
10 BORON NITROGEN COMPOUNDS
give three-coordinate PV centers (see (40); equation 16). 1.509(8) 1.535(8) A for the hydrogen-bonded groups). The
dissociation enthalpy for a pyridine complex of [B(N3 )3 ] was
Me t-Bu calculated to be 10 kcalmol1 .76
(Me3Si)2N P + (Me3Si)2N B
R N3 N3 N
N2
(i-Pr)2N B (i-Pr)2N B
N2
P(SiMe3)2 P SiMe3
(14)
Me3Si
Me t-Bu
(Me3Si)2N P N B dimer
N(SiMe3)2 (17)
R
(39) SiMe3
Me3Si P N(i-Pr)2
NMe2 t-Bu N B
Me2N P + (Me3Si)2N B
B N
Ph N3 N2 (i-Pr)2N P SiMe3
(15) SiMe3
Ph t-Bu
Me2N P N B The gas-phase molecular structures of Me2 BN3 and
NMe2 N(SiMe3)2 Me2 BNCO have been determined by electron diffraction.77
The BN3 and BNCO units are planar and bent. MO calculations
t-Bu for the B-azido compound reproduce the observed bent
(Me3Si)2N P ESiMe3 + (Me3Si)2N B structure, but they predict a linear structure for the B-
N3 isocyanato analog.
N2
(16)
ESiMe3
t-Bu
7 CATIONIC SPECIES
(Me3Si)2N P
N B
N(SiMe3)2 Examples of tetra-coordinate boronium ions (41) have been
E = CH, N
(40) known for many years.78 The quest for low-coordinate, neutral
borane compounds also stimulated interest in the formation
The reaction of i-Pr2 NB(Cl)P(SiMe3 )2 with Me3 SiN3 gives of three-coordinate borenium ions (42) and two-coordinate
a stable azido borane iPr2 NB(N3 )P(SiMe3 )2 ,49 which when borinium ions (43).7880
heated in vacuo at 80 C produces nitrogen. The incipient
nitrene dimerizes accompanied by silyl group migration from
phosphorus to nitrogen (equation 17). The (PBN)3 ring H3N H R
B+ B D+ R B D+
has a boat conformation, and the decomposition pathway
H3N H R
resembles that reported for R2 BN3 species that produce
(41) (42) (43)
borazines (RBNR)3 .1 In contrast, use of the C6 F5 group
in a similar reaction allows for the structurally characterized
diamer [(Ar)2 B(N3 )]2 . X-ray diffraction studies have shown The cations are typically prepared by (1) boron-halogen
a BN bond length of approximately 1.59 A.74 The bis- bond heterolysis (for example, by displacement of Br by
azido compound, C6 F5 B(N3 )2 , is readily prepared through pyridine to form [BF2 (py)2 ]+ ),81 (2) electrophilic attack on BN
a TMSCl elimination reaction. It can be isolated as the bonds, (3) nucleophilic displacement, or (4) metathesis (for
pyridine adduct, but in the absence of base, will trimerize example, by silanol elimination from the chelate B(OSiPh3 )
in the solid state.75 In a recent breakthrough for this with trific acid to acid to form [LB(thf )]+ OTP ).82 The
chemistry, crystal structures of [B(N3 )3 ]x L (L = quinoline, cationic B center is stabilized by amino substituents, which
X = 1 and L = pyrazine, X = 2) and [B(N3 )4 ] (isolated as donate to boron, and by bulky substituents. The formation of
the 2,2,6,6-tetramethylpiperidinium salt) were reported. B- cations with electrophilic reagents in fact suggests that some
Nquin was found to be 1.619(2) A and BN was found to be previously studied reactions of boranes may proceed through
approximately 1.52 A in the quinoline derivative. [B(N3 )4 ] cationic intermediates as opposed to neutral coordination
demonstrated variable BN distances, depending on whether complexes. For example, Ph2 B(ClO4 ) catalyzes aldehyde
the -nitrogen was involved in hydrogen bonding (BN of condensations.83 Although it has a polar covalent BO bond
1.529(7) 1.549(6) A for the nonhydrogen-bonded groups and in nitromethane (having a 11 B NMR shift of 46 ppm),84 it
BORON NITROGEN COMPOUNDS 11
is likely to be cationic in the presence of the aldehyde. NH3 have been examined,91,92 and Kimura92 has succeeded
Borenium salts are obtained from n-Bu2 B(O3 SCF3 ) and 9- in isolating (H2 NBNH)3 (44), which rapidly polymerizes with
BBN(O3 SCF3 ) when combined with sterically demanding loss of NH3 .
bases, while neutral acid-base complexes are obtained with
less demanding bases. Neutral complexes are also obtained
with n-Bu2 BCl and 9-BBNCl. Several adducts of R2 BClL NH2 Ph Me Ph
produce borenium ions when combined with AlCl3 or GaCl3 . B Me B Me N B
HN NH N N
Similarly, SbCl5 abstracts Cl from Ph2 BCl in CD3 NO2 to Cl Ti Cl Ph B
form a transient cation having a 11 B NMR shift of 20 ppm.85 B B Ti N
H2N N NH2 N
H Cl Cl Cl3Ti TiCl 3
Me N
(44) (45) (46)
8 BORAZINES
In a parallel area, and as part of the effort to deve-
Borazines, (RBNR)3 , can be considered to be cyclotrimers lop polymers suitable for formation of ceramics and
of parent iminoboranes, RBNR.8688 In general the ceramic composites, Roesky93 has reported formation
compounds are relatively stable, and as a result they can of several metalloborazines. For example, reactions of
be obtained through many routes. In fact, they are often MeN[PhBN(Me)SiMe3 ]2 with TiCl4 produce nonplanar
undesired side-products or decomposition products. The bicyclic rings such as (45) and (46).
simplest borazine, (HBNH)3 , is often referred to as inorganic
benzene, a correspondence that is probably overemphasized.
The compound displays D3 h symmetry with equivalent,
relatively short BN bond distances of 1.44 A. The 1 H 9 PYRAZABOLES
NMR data for substituted borazines suggest some degree
of transannular electronic conjugation. However, reactivity
Pyrazaboles of the general types represented by (47) and
patterns of borazine differ markedly from benzene. For
(48) have been under study for a number of years, and the
example, borazine takes part in little electrophilic substitution
syntheses of numerous derivatives have been reviewed.87,94,95
chemistry, but does undergo many addition reactions. These
The compounds are relatively stable, and a significant body
observations suggest that borazine reaction chemistry is more
of C-atom organic substitution chemistry has been developed.
dictated by BN bond polarity than the HOMO/LUMO
In addition, the anionic character of (47) has made these
character of the molecule. Needless to say, these divergent
species particularly attractive ligands for both metal and
pictures have led to a number of experimental and theoretical
nonmetal cations. That topic is summarized in Section 10
studies of the electronic structure of borazine.89,90 The current
of this article.
view appears to favor a picture in which the system is highly
polarized, but significantly resonance stabilized.
Borazine is often prepared by reaction of NH4 Cl R R
and LiBH4 or NaBH4 , or by thermal decomposition of
H3 BNH3 . Trichloroborazine, (ClBNH)3 , is prepared by R N N R X N N X
combination of BCl3 and NH4 Cl. Both compounds undergo R
B B B B
a variety of substitution reactions at boron. It is often N BR4x R N N R X N N X
straightforward to obtain complete substitution, for example, N
(XBNH)3 , but difficult to obtain mono- or disubstitution x
R R
products, (XB) (HB)2 (NH)3 and (XB)2 (HB) (NH)3 , in
(47) (48) (49)
pure form. Many N-substituted borazines are obtained by
using substituted amines or ammonium halides. Again,
complete symmetrical substitutions, for example, (HBNR)3 or Niedenzu initiated studies of B-substituted analogs of
(ClBNR)3 , are usually straightforward; however, incomplete (47) and (48) and various X = chloro, fluoro, alkyl, aryl,
or asymmetrical substitutions are difficult. The majority of alkoxy, and amido derivatives of (49).96 These compounds
available substitution possibilities have been summarized.87 should be very useful for further synthetic transformations.
The recent interest in boron nitrogen-containing polymers Koster and coworkers97,98 have examined the reactions
has spurred some renewed interest in borazine preparations of sterically congested pyrazoles with (9H-9-BBN)2 and
since these compounds are potential monomers. The unique neutral, monomeric products with tricoordinate boron
direct reaction between (ClBNH)3 and NH3 produces an centers (50) are obtained. The compounds are stable toward
organic solvent insoluble polymer. In an attempt to control dimerization. When bulky pyrazoles are allowed to react
ammonolysis chemistry, the reactions of (Me2 NBNH)3 with with activated trialkylboranes, for example, BEt3 at 170 C,
12 BORON NITROGEN COMPOUNDS
a monomeric pyrazoleborane (51) is obtained. At 220 C the and only a few recent advances are summarized here for
t-Bu group is likely to undergo beta-hydride elimination, illustrative purposes. The HB(pz*)3 K ligand, in combination
and the alkene intermediate may undergo hydroboration with PCl3 , gives rise to [HB(pz*)3 ]PCl2 in which the
with resultant formation of a C-borylated pyrazoleborane ligand is likely to be bonded in a trihapto fashion to
dimer (52). the P atom. Subsequent reaction with Na2 Fe(CO)4 gives
[HB(pz*)3 ]PFe(CO)4 , a complex containing a novel terminal
phosphinidene ligand.105 Parkin106,107 has reported the use of
other C-alkylated HB(pz*)3 K and H2 (pz*)2 K salts to form
B BEt2 a new set of complexes with Al, Mg, and Be. Niedenzu108
N N N N and Reger109 have reported tin(II) complexes while using
H2 B(pz) , H2 B(pz*)2 , B(pz)4 , and B(pz*)4 .
t-Bu t-Bu t-Bu t-Bu
Many new transition metal complexes of these ligands
R R continue to be prepared. The most interesting aspects of
this chemistry are not so much the evolution of specific
(50) (51) new ML, ML2 , and ML3 compositions, but the purposes
that the ligands serve or are suggested to serve. For
example, poly(pyrazolyl)borate anions have been used to
2+
stabilize a 17-electron radical fragment, a seven-coordinate
WII complex, half-sandwich HB(pz*)MCl compounds, and
to mimic a variety of natural bioinorganic coordination
N N
Et conditions.110112
B B
N N Et
The reaction of several examples of (56) with H3 BTHF for ketone reductions, asymmetric allylations, Diels Alder
produces a novel four-membered bicycle represented by reactions, and aldol condensations.122
(60).117
R H H H 12 BORON NITRIDE
B
N B
N B B R B B R Extending the BN/CC analogies employed throughout
R B B R N
B N this article, it is found that the allotropes of BN have a
N
close correspondence with those of carbon. For example,
R R the hexagonal form of BN forms a layered structure related
(58) (59) (60) to graphite, and the cubic form of BN closely resembles
diamond. A number of properties for the two materials are
similar but, interestingly enough, some properties are quite
The substitution of BN for a C=C unit in pyrrole different. These differences include color, electrical properties,
gives a class of diazaboroles (61). Some of the most recent and optical properties. Practical interests in various forms
advances involving this ring, including -complexes with the of BN have spurred significant growth in boron nitrogen
Cr(CO)3 fragment and a potassium salt, have appeared.118 The monomer and polymer chemistry. A thorough review of BN
reactivity of four-membered diazadiboretene rings continues appeared in 1990,123 and aspects of the synthesis of BN from
to be of interest, and a recent paper summarizes the variety preceramic polymers were updated in brief reviews appearing
of larger rings that can be prepared via insertion reactions on in 1991124 and 1992.125 The present growth in this area
(t-BuNBR)2 .119 Koster and coworkers120 explored in some should continue as new applications for the material are made
detail the reactions of Et3 B, i-Pr3 B, and t-Bu3 B with a possible by the availability of processible precursors and new
family of alkyl cyanides at 200 C. A variety of heterocycles, synthetic techniques.
including (62), (63), and (64), was produced, and the specific Within this section, it is appropriate to point out that
products obtained depended on the alkyl groups on the there is interest in preparing isoelectronic BN analogs of
borane, the cyanide, and the reaction conditions. In another the newest form of carbon, C60 ,126,127 and this offers a
study, reactions of (Me2 N)2 BR with dimethylurea were found challenge to molecular chemists interested in this area of
to give bicyclic species of the general type represented inorganic chemistry.
by (65).121 Boron nitride can be prepared by many routes such
as CVD (NH3 + organoborane),128 pyrolysis of preceramic
H R polymers derived from borazine,129 and solid-state metathesis
(NaBF4 + 3NaN3 , for example).130,131 The type of BN formed
Et N in these reactions parallels the materials that can be obtained
Et
B B from carbon. Thin films and coatings of BN have been studied
R N N Et N Et extensively.132 BN nanotubes can be prepared by CVD at
B R
1100 C using borazine (see Section 8) and catalytic NiB2 .133
R H R The tube formation is proposed to occur through a root-growth
(61) (62) mechanism where growth occurs at the tube-catalyst interface.
A low-temperature route (450 600 C) to BN nanotubes using
NH4 BF4 , KBH4 , and NaN3 has recently been reported.134 They
O
have a diameter range of 60 to 350 nm. Hexagonal BN onions
R R and other structures can be prepared by combining BBr3 with
RN NR NaNH2 and NH4 Cl at approximately 400 C.135 The materials
B R R R R
HN NH B were characterized by XRD, FT-IR, XPS, and EDXA spectra.
HN NH B
R B B R Using activated carbon as a template, activated BN was
synthesized with a specific surface area of 168 m2 g1 , a total
RN NR
C pore volume of 0.27 cm3 g1 and an average pore radius of
N O 32.2 A.136 Spherical particles of 50 to 400 nm in diameter have
been prepared through thermolysis of trimethoxyborane under
(63) (64) (65)
an ammonia atmosphere.137 BN fibers138 and nanowires139 are
also known.
Finally, it is noted that some utility is being found for some BN materials have many potential applications beyond
of these apparently esoteric ring compounds. Oxozaboro- use in ceramics. For example, the vacuum pyrolysis of
lidines and dioxaborolidines serve as enantioselective catalysts poly(4,6-borazinylamine) produces highly microporous BN
14 BORON NITROGEN COMPOUNDS
with surface areas of 53 to 696 m2 g1 and pore volumes 18. V. M. Norwood III and K. W. Morse, Inorg. Chem., 1988, 27,
of 0.036 to 0.39 cm3 g1 . Since BN has an inherently polar 302.
surface, porous BN should be an ideal gas adsorbent.140 19. M. Mittakanti and K. W. Morse, Inorg. Chem., 1991, 30, 2434.
Indeed, BN nanotubes are capable of storing H2 at ambient 20. M. R. M. D. Charandabi, D. A. Feakes, M. L. Ettel, and
temperature.141 Hexagonal BN can serve as a template for K. W. Morse, Inorg. Chem., 1991, 30, 2433.
diamond synthesis.142
21. W. J. Mills, C. H. Sutton, M. W. Baize, and L. J. Todd, Inorg.
Chem., 1991, 30, 1046.
22. C. H. Sutton, M. W. Baize, W. J. Mills, and L. T. Todd, Inorg.
Chem., 1992, 31, 4911.
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23. B. F. Spielvogel, A. Sood, B. R. Shaw, and I. H. Hall, Pure
Appl. Chem., 1991, 63, 415.
Boron Hydrides; Boron: Inorganic Chemistry; Boron:
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Boron: Organoboranes desired octet configuration either through -overlap with
a substituent X or through formation of neutral or ionic Lewis
acid Lewis base complexes (Figure 1). These interactions have
Frieder Jakle been exploited in many of the applications of organoboron
Rutgers University, Newark, NJ, USA compounds. For example, overlap of the empty p-orbital on
boron with organic -systems leads to interesting luminescent
and nonlinear optical properties. In addition, the selective
coordination of nucleophiles D has opened a new avenue to
1 Introduction 1 sensor materials. Indeed it is this donor acceptor interaction
2 General Synthetic Methods 1 that allows organoboron compounds to act as efficient catalysts
3 Alkylboranes 6 and cocatalysts in organic synthesis. Moreover, intramolecular
4 Alkynylboranes and Vinylboranes 9 donor acceptor interactions are ubiquitous in the design
5 Boron Attached to Unsaturated Organic Rings 10 of new heterocycles, and intermolecular interactions permit
6 Boron as Part of Unsaturated Organic Rings 18 the (reversible) assembly of macrocycles and coordination
7 Selected Applications of Organoboranes 22 polymers. Finally, organoborates, BR4 , have been studied
8 Related Articles 32 extensively as weakly coordinating anions and are useful,
9 References 32 for example, as battery components and cocatalysts in olefin
polymerization.
This chapter reviews these new developments and strives to
provide an overview of the current state of the highly interdis-
Abbreviations ciplinary field of organoboron chemistry. The focus will be on
the synthesis, structural aspects, properties, and applications
9-BBN = 9-borabicyclo[3.3.1]nonyl; cat = Catecholato;
of new organoboron compounds. Although reference to a few
cod = 1,5-cyclooctadiene; coe = Cyclooctene; Dur =
specific and particularly important applications in organic syn-
Duryl = 2,3,5,6-tetramethylphenyl; Fc = 1-ferrocenyl; fc =
thesis will be made, the broad applications of organoboranes
1,1 -ferrocenediyl; Ipc = Isopinocampheyl (derived from (+)-
as reagents in organic synthesis cannot be covered in the con-
-pinene); Mes = Mesityl = 2,4,6-trimethylphenyl; Np =
text of this review. However, there are ample recent reviews
2-naphthyl; OLED = Organic light-emitting diode;
and texts that the interested reader is referred to (general;14
Pf = Pentafluorophenyl; pin = Pinacolato; SCE = Standard
organoboron reagents,513 organoboron catalysts,1419 cou-
calomel electrode; thexyl = 2,3-dimethyl-2-butyl; TMP =
pling reactions2023 ). A separate chapter specifically devoted
2,2,6,6-tetramethylpiperidide; tripyl = 2,4,6-tri-iso-propyl-
to boron nitrogen compounds (see BoronNitrogen Com-
phenyl.
pounds) gives information on the important classes of amino-
substituted organoboranes and organoborane amine adducts.
The beginning of the chemistry of organoboron compounds A brief overview of some of the most important
dates back to 1859 when Frankland discovered triethylborane, synthetic routes to organoboranes, that is, (1) transmetallation
Et3 B. While the subsequent availability of Grignard reagents reactions, (2) the boration of unsaturated compounds, and
provided facile access to organoboranes, a major breakthrough (3) CH activation will be given. General aspects of
was the discovery of the hydroboration of alkenes as these methodologies will be covered and illustrated with
a convenient entry point to organoboron chemistry by selected recent literature examples. While a large number of
Brown in 1956. Over the past decade the chemistry of transformations are known that convert one boron compound
organoboron compounds has developed from an area primarily to another, the diversity of these methods does not allow for
of interest with regard to organic synthesis applications, where full treatment in this context. Detailed information is given
organoboranes play a pivotal role both as reagents and as in several excellent comprehensive reviews that have been
catalysts, into a highly interdisciplinary research field. published.13
Of particular significance in the chemistry of organoboranes
is their behavior as Lewis acids, which is a result of the
empty p-orbital of tricoordinate boron. Much recent effort 2.1 Organometallic Precursors
has been devoted to the synthesis and development of highly
Lewis-acidic organoboron compounds through introduction Transmetallation reactions represent an important method
of fluorinated organic substituents. Boron can reach the for the synthesis of organoboranes.13 Organometallic
2 BORON: ORGANOBORANES
D 1. 2 n-BuLi
S 2. 2 Mes2BF S
R Mes2B BMes2 (5)
R R S
B R B X B B 2
R R R R
R R R R 1. K; THF/NEt3
2. ClB(NMe2)2 B(NMe2)2 (6)
1. 3 n-BuLi
2. BF3. OEt2
3 Br B n n
BBr3
(7)
CH2Cl2
24 h, r.t.
(4) SiMe3 BBr2
BORON: ORGANOBORANES 3
BCl3
Organomercury, organozinc, and organocopper reagents
CH2Cl2
have been successfully employed in many cases, in
(8)
Me3Si Sn 78 C Me3Si B which other more readily accessible reagents did not
Bu Bu
Cl give satisfactory results. Some examples are illustrated
in equations (14 16).38,39 Reactions involving aluminum
BCl2 and zirconium boron exchange (organozirconium chemistry:
Mes BCl3
Fe Fe (9) see Zirconium & Hafnium: Organometallic Chemistry)
Sn toluene
Mes have also been reported, and representative transformations
0 C
SnMes2Cl are shown in equations (17) and (18). In particular, the
Mes Mes commercially available trimethylaluminum is frequently used
B [Li(THF)4]+ Mes2B BR2 as a convenient methyl group transfer reagent.40 Alkyl and
vinylzirconium species, which are conveniently obtained
R2BBr (10) via hydrozirconation or zirconocene coupling reactions,
Et2O
25 oC
react smoothly with boron halides under zirconium boron
R = Me, Ph
exchange.41,42
(8)
A large number of hydroboration reagents are available
ranging from borane adducts BH3 D (D = Me2 S, THF, NR3 ,
Arylboranes, ArBH2 and Ar2 BH, have been studied as an
PR3 ) to in situ generated haloboranes X2 BH. Organoboranes
alternative to alkylboranes in order to avoid potential problems
RBH2 and R2 BH are also frequently used and often give
related to retrohydroboration reactions. Moreover, further
higher selectivity in hydroboration reactions. Moreover, the
stabilization may be readily achieved by 2,6-disubstitution
use of chiral substituents on boron provides an opportunity
on the phenyl ring. Smith and Pelter reported the synthesis
for enantioselective catalysis.57 Some of the most commonly
and properties of mesitylborane (9) and tripylborane (10).46
used organoborane reagents are shown (112) and recent
Mesitylborane (9), which is obtained from Mes2 BH (11)
developments will be outlined in the following.
and BH3 THF, shows not only better stability in solution
compared to thexylborane (2), but also exhibits very high
regio- and chemoselectivity in hydroboration reactions.
Polymer-supported versions of these arylboranes have been
MeBH2 BH2 BH2 developed.47
R
H
R BH2
B B H
BH
R
2
(4) (5)
R = Me (9)
R = i-Pr (10) (11)
Chiral alkylhaloboranes RBHX that are even more effi-
cient than typical organoboranes RBH2 and R2 BH were
developed by Brown. For instance, isopinocampheylhalobo- The fluorinated diarylborane (C6 F5 )2 BH (12) and its
ranes (6; IpcBHX, X=Cl, Br) and related 2-organylapopinene hydroboration activity were studied by Piers.48,49 This
BORON: ORGANOBORANES 5
2 ClB(C6F5)2
2 Me2SiCl(H)
R3M+
R3B
R3M R R BR3
[HB(C6F5)2]2 2HB(C6F5)2
(12)
2 Et3SiH R3M BR2 R3M R
2 B(C6F5)3
or
R R R BR2
Scheme 1
Et3B Me3Si Et
Haloboration Reactions. The haloboration of car- Me3Si SiMe2H
bon carbon triple bonds provides another entry point for Me2Si BEt2 (23)
the synthesis of organoboranes.2,13,51 A wide variety of H
haloboranes including BBr3 , 9-BBN-Br, and 9-BBN-I has (14)
been found to react with terminal alkynes to produce (Z)-
2-halo-1-alkenylboranes.13 The reaction occurs in a stereo-, Catalyzed Boration Reactions. Since the initial report
regio-, and chemoselective fashion specifically with terminal by Mannig and Noth on the rhodium catalyzed room
alkynes and has been used to synthesize numerous substi- temperature addition of HBcat to alkenes much effort has
tuted olefins and related compounds. Diboration reactions of been devoted to the search for new catalytic hydroboration
alkynes with B2 Cl4 are also well known. However, more con- processes and other boration reactions (see Hydroboration
venient transition-metal-catalyzed procedures with the less Catalysis).7,54,55 The most intriguing aspect of transition-metal
reactive alkoxy substituted diboranes B2 (OR)4 have recently catalysis in boration reactions is that (1) chemoselectivity,
been developed. (2) regioselectivity, and (3) stereoselectivity may be altered
compared to uncatalyzed reactions. New methods for the
1,1-Organoboration Reactions. Alkynyl derivatives catalytic addition of diboranes R2 BBR2 ,56,57 BS,58 BSi,59
R3 MCCR of the group 14 elements (M=Si, Ge, Sn, Pb) and BSn60 moieties have greatly enhanced the scope and
react with organoboranes R3 B via 1,1-organoboration to give utility of catalytic boration chemistry. Moreover, cross-
boron-substituted alkenes (Scheme 2).52 In most cases, high coupling of BB and BH compounds with organic halides
yields and good selectivity are observed for products with the and triflates provides a convenient one-step procedure for
R2 B group and the group 14 element in cis-position at the the synthesis of organoboron compounds from organic
carbon carbon double bond. electrophiles.5557 For many of these catalytic processes,
Organoboranes typically used in these reactions are Et3 B, i- boryl metal species have been identified as key intermediates.
Pr3 B, and alkylated 9-BBN derivatives. Interestingly, multiple The transition-metal-catalyzed diboration of alkynes can
organoboration steps may take place with di-, tri-, and tetra- be directed to give highly selective cis-addition yielding 1,2-
1-alkynyl element compounds. Intermediates such as the diborylated olefins (equation 24). Depending on the catalyst,
6 BORON: ORGANOBORANES
R1 R2
82% 88%
B2pin2
R1 R2
[Pt(PPh3)4]
O B B O
Scheme 3 Borylation of arenes via CH activation
O O
reported.70,71
(24)
BBr2
2 BBr3
2.3 CH Activation Fe Fe (27)
hexanes
reflux
BBr2
A new direct access to organoboranes via stoichiometric
and catalytic CH activation (see Alkane CarbonHydrogen On the other hand, transition-metal catalysis provides
Bond Activation) has been developed over the past few an opportunity to regioselectively borylate even electron-
years.62 It is especially interesting that this methodology poor aromatic compounds under mild conditions and in
provides an opportunity to functionalize unreactive CH bonds the presence of functional groups. The first example of
of hydrocarbons in a single preparative step thus combining transition metal catalyzed aromatic CH borylation was
economy, efficiency, elegance, and environmental benignity.62 reported in 1993, when Marder found borylation of the
Most studies have been performed with diboranes such as solvent toluene during the preparation of the iridium boryl
B2 (OR)4 , but boranes HB(OR)2 may also serve as a precursor. complex Ir(6 -MeC6 H5 )(Bcat)3 from Ir(5 -C9 H7 )(cod) with
Initial reports on the borylation of alkanes using catecholborane (catBH).72 The first catalytic process has
isolated transition-metal boryl complexes date back to 1995, been reported by Smith, who used iridium complexes
when Hartwig showed that Cp Re(CO)2 (Bpin)2 converts containing phosphine ligands.73,74 Various rhenium and
pentane to 1-borylpentane with high regioselectivity.63,64 The rhodium complexes have since been shown to catalyze the
catalytic CH borylation of alkanes with Cp Re(CO)3 using aromatic borylation with B2 pin2 and HBpin, respectively.
photochemical activation was demonstrated soon thereafter More recently, Miyaura and Hartwig have demonstrated the
(equation 25).65 Also, an efficient thermal process that room temperature conversion of arenes to arylboranes with
involves the use of rhodium catalysts has since been developed B2 pin2 in the presence of the iridium complex [Ir(OMe)(cod)]2
(equation 26).66 It is interesting to note that this methodology and the ligand di-t-butylbipyridine (dtbpy) as shown in
is not restricted to small molecules, but has recently Scheme 3.57,75,76
been exploited for the direct side-chain functionalization of Marder reported that the alkyl CH bonds in benzylic
polyolefins.67 compounds are selectively borylated with a rhodium
catalyst.77 Aromatic borylation products were only observed
as minor by-products. Similar results were obtained by
Cp Re(CO)3 Miyaura with Pd/C (equation 28).78
pin2 B2 + HR pinBR + pinBH (25)
h/CO
Pd/C 3 6 mol% 2pinBCH Ph
Cp Rh(4 -C6 Me6 ) pin2 B2 + 2PhCH3 2
+ H2 (28)
pin2 B2 + 2HR 2pinBR + H2 (26)
100 C/16 h 74%
150 C
has a melting point of 112 K, has been determined only very (1923)).86,87 Interestingly, depending on the catalyst, the
recently.79 In contrast to its heavier group 13 analogues, diboration of vinylboranes with B2 cat2 leads via sequential
it consists of layers containing only extremely weakly diboration and dehydroboration steps either to 1,1,1-
interacting BMe3 molecules. The shortest intermolecular triborylalkanes (20) or to 1,1,2-triborylalkanes (21).88 1,1,1-
B H contact is 3.04 A, which is well beyond the sum Triborylalkanes, 1,1,2,2-, and 1,1,1,2-tetraborylethane species
of the van der Waals radii of B and H (2.83 A). have been proposed as intermediates in the reaction of
Numerous higher alkylboranes have been prepared and are borylated alkynes with excess Et2 BH (hydride bath) that
commonly encountered as intermediates in synthetic organic eventually leads to the formation of small carboranes.8991
chemistry.1,2,5,7,8,10,12,20,22 Indeed, isolated triborylmethane species with alkyl or halide
Perfluorinated analogs of trialkylboranes, tris(trifluorome- substituents on boron have recently been shown to rearrange
thyl)borane (B(CF3 )3 ; 15) and its higher homologs, are to small carboranes upon thermal treatment.87
still unknown although they have been the subject of a Tetraborylmethane derivatives continue to attract interest
considerable research effort.80 Many complexes of (15) on as potential candidates for the stabilization of planar
the other hand have been isolated.81 Indeed, the BN bond tetracoordinate carbon.92 Species C(B(OR)2 )4 containing
in amine adducts is extraordinarily stable and withstands alkoxy substituents on boron adopt classical structures.
even hydrochloric acid and concentrated solutions of KOH. However, a planar tetracoordinate carbon environment has
However, the donor-free compound (15) could not be been suggested based on DFT calculations for compounds
liberated. This is believed to be due to facile decomposition C(BR2 )4 (R = alkyl), in which the CB4 group is incorporated
under elimination of difluorocarbene and formation of BF3 . into a cage system thus leading to both electronic and
The unusual organoboron carbonyl complex (CF3 )3 BCO mechanical stabilization.93,94 The electronic structures of
(16) has been prepared very recently.82 This complex was penta- and hexaborylated compounds containing planar
obtained in high yield through solvolysis of the borate salt pentacoordinate and hexacoordinate carbon have also been
K[B(CF3 )4 ]83 in concentrated sulphuric acid and was found studied using theoretical calculations.95,96
to be exceptionally stable. In contrast, (C6 F5 )3 BCO needs to Numerous cyclic organoboranes are known and only
be generated in a CO matrix and is only stable at very low selected recent studies will be highlighted. 1-Boraadamantane
temperature. A rich chemistry has been developed with the (24), which is isoelectronic with the 1-adamantyl cation, is
aminoborane (CF3 )2 BNMe2 , which serves as a precursor to a peculiar trialkylborane since the three-coordinate boron
other trifluoromethylborane complexes (CF3 )2 BRD (R=H, atom normally prefers a trigonal planar environment, but
alkyl, aryl) and numerous heterocyclic compounds.80
Diborylated organoboranes with a BCB backbone such
as (17) are usually prepared by double hydroboration 1. 2 HBCl2
Bcat
2. 2 catechol
of terminal alkynes (equation 29).84 The treatment of the t-Bu Bcat Bcat
diborane B2 pin2 with diazomethane derivatives provides an t-Bu Bcat
interesting alternative that allows for the synthesis of species (19)
pinBCR2 Bpin (18, R=H, Ph; equation 30), which are not
Bcat Bcat
accessible via hydroboration reactions.85 B2cat2
[(Ph3P)3RhCl] Bcat
Ar Ar Bcat
H
2HBcat (20)
R H Bcat (29)
R Bcat catB H
Bcat B2cat2
(17)
[Rh(COE)2(m-Cl)]2 Bcat
Ar Ar Bcat
R R R 2 P(o-tol)3
Pt(PPh3)4 (21)
B2pin2 + C N2
(30)
80 C pinB Bpin
R
(18) catB Bcat
catB Bcat H2 H
Pd/C H
Compounds containing three or even four boryl groups catB Bcat catB Bcat
attached to a single carbon atom are accessible through (22)
treatment of RCCl3 with ClB(OR)2 and lithium metal, a
catB Bcat
synthetic route that has been thoroughly studied by Matteson 2B2cat2
catB Bcat Bcat
in the 1970s. Moreover, 1,1,2,2-tetraborylethanes are obtained [(Ph3P)2PtC2H4] catB
in good yields from acetylene and B2 Cl4 . More recently, toluene, reflux catB Bcat
(23)
transition-metal-catalyzed hydrogenation, hydroboration and
diboration reactions have been used to prepare triborylalkane,
tetraborylethane, and hexaborylethane derivatives (Scheme 4, Scheme 4
8 BORON: ORGANOBORANES
Me3Si SiMe3
Cl Cl 2LiCH2SiMe3
B B B B
Dur Dur Dur Dur
1. 2LiNMe2
2. 3B(OMe)3
3. BCl3
R Cl
Me3Si B R Me3Si B H
H
H C C
SiMe3 H
C
SiMe3
C
B B B B
Dur Dur Dur Dur
2 Li 2Li
2
R
B Me3Si B H
Me3Si H R
H C C
SiMe3 H
C C
SiMe3
B B B B
Dur Dur Dur Dur
2 Li+ Li+
Scheme 6
BORON: ORGANOBORANES 9
(42)
Siebert also used the cobalt-mediated cyclization of alkynes
to synthesize the first tetraborylated and hexaborylated
Scheme 9
benzene compounds (4850; Scheme 10). The boronate
ester (49) which formed initially was converted into the
1,2-C6 F4 (SnMe3 )(BCl2 ) (41) was detected initially, the intriguing base-free hexafunctional triorganoborane (50) with
expected diborylated intermediate 1,2-C6 F4 (BCl2 )2 was not trimethylaluminum.112,121
observed at any time during the reaction. It was suggested that The starting point for the synthesis of peri-borylated
the decreased nucleophilicity of the perfluoroaryl compounds naphthalenes is 1,8-dilithionaphthalene, which may also
disfavors the second electrophilic aromatic substitution step be transformed into other useful reagents such as 1,8-
relative to coupling. The diborylated species C6 F4 (BBr2 )2 can distannylated and 1,8-dimercuriated naphthalenes.31 Since
on the other hand be prepared from the mercurated precursor the initial report of Katz on the unusual properties of 1,8-
(1,2-C6 F4 Hg)3 as shown in equation (14).38 Perfluorinated bis(dimethylboryl)naphthalene (51) as a hydride-sponge new
arylboranes are further discussed in the context of their use as
olefin polymerization activators in Section 7.3.3. Moreover,
diboraanthracenes (40) and related diboracycles (43), (44) and O O
(45) (X = Cl, Me, NMe2 ), which are readily available through B B
tin boron exchange reactions, have been extensively studied O O
as ligands for transition-metal complexes.101
[CpCo(CO)2]
X X X
B BCat BMe2
B R B R
R CatB BCat Me2B BMe2
Me3Al
H R
B R B B
X CatB BCat Me2B BMe2
X X
BCat BMe2
(43) (44) (45) 67%
(49) (50)
research has been devoted to the exploration of this class of electrochemical studies. A more extensive exchange inter-
bidentate Lewis acids (see also Section 7.2).31 New derivatives action was observed between vanadium centers in related
such as the phenyl-substituted (52) and the amino-substituted trovacenylboranes Mes3n B[(7 -C7 H7 )V(5 -C5 H4 )]n (59).132
species (53) have been synthesized (equation 34).31 The latter Finally, tetraarylborates have been used for the generation of
form B2 N2 four-membered rings when small substituents are zwitterionic transition-metal complexes and of borato-bridged
attached to the amino groups.126 complexes, in which one or two aryl groups of the Ar4 B
moiety bind to the metal.133,134
Li Li R2B BR2 It is interesting to note in this context that arylboron
transition-metal complexes with metal boron bonds have
R2BX recently been structurally confirmed. Transition-metal boryl
(34) complexes have been of intense research interest, partly
because of their involvement in the hydro- and diboration
(51) R = Me of carbon carbon multiple bonds, but also owing to their
(52) R = Ph
(53) R = NR2
importance in the stoichiometric and catalytic functional-
ization of alkanes and arenes under thermal and photolytic
conditions (see Alkane CarbonHydrogen Bond Activa-
It is interesting to note that the reaction of 1,8-
tion).135138 While various borane and borylene complexes
dilithionaphthalene with diorganoboron halides does not
that feature amino substituents are known, only a few struc-
always lead to diborylated naphthalene species. The
turally confirmed arylborane complexes have recently been
antiaromatic cyclic 16- -electron system (54) and the
described.138 Reaction of [CpFe(CO)2 ]Na with BrB(C6 H5 )2
strained four-membered ring (55) formed upon reaction of
and ClB(C6 F5 )2 , respectively, led to attachment of diphenylbo-
dilithionaphthalene with (C6 F5 )2 BFOEt2 and Mes2 BF in
ryl and bis(pentafluorophenyl)boryl groups to the CpFe(CO)2
diethyl ether, respectively (Scheme 11).31,127 The boracycle
fragment in complexes (60) and (61).139,140 The FeB dis-
(55) serves as a precursor to other 1,8-disubstituted
tance in the perfluorinated derivative (61) (two independent
naphthalenes through ring-opening reaction with electrophiles
molecules: 1.965(5) and 1.964(4) A) is significantly shorter
such as Ph2 BBr or Me3 SnCl (see equation 10).128,129 Other
than that in the phenyl species (60) (2.034(3) A). This effect
extended systems that have been borylated include
has been attributed to the higher Lewis acidity of the boron
biphenylene and anthracene.25,130 The borylated derivatives
center, which in turn results in increased -overlap between
are typically obtained from lithiated species via treatment
boron and iron. The synthesis of the first terminal and bridging
with Mes2 BF.
arylborylene complexes (62) and (63) has also recently been
The aromatic moiety in phenylboranes and phenylb-
reported (Scheme 12).141,142
orates may serve as a 6-electron donor ligand
to transition-metal complexes. Half-sandwich complexes
of chromium, Mes2 [B(6 -Mes)Cr(CO)3 ] (56), MesB[6 - 5.2 Cyclopentadienylboranes
MesCr(CO)3 ]2 (57), and B[6 -MesCr(CO)3 ]3 (58), containing
trimesitylborane as a ligand have been prepared and struc- The attachment of boryl groups to cyclopentadiene, indene,
turally characterized.131 The Cr(CO)3 moieties interact weakly and fluorene has attracted much interest over the past decade
in the multinuclear systems (57) and (58) as shown by owing to their utility as precursors to borylated transition-metal
complexes, most notably those of group 4. The preparation
of cyclopentadienylboranes from organolithium, Grignard, or
Li Li
organotin precursors with boron halides is well established.
(C6F5)2BFOEt2 Cyclopentadienylboranes exist as three constitutional isomers,
which can interconvert through sigmatropic rearrangements.
Upon preparation at low temperature, the allylic isomer (64)
F is obtained initially. This isomer is fluxional as a result of fast
Mes2BF sigmatropic migration of the BR2 group if alkyl substituents
F F
are attached to boron. Upon warming to room temperature
Mes Mes C6F5 a mixture of the thermodynamically favored vinylic boranes
B F B (65) and (66) is formed via a [1,5] sigmatropic hydrogen
shift.143 The deprotonation of cyclopentadienylboranes was
studied with the aim of developing convenient precursors
for transition-metal complexes. Intriguingly, Herberich found
(55) (54)
that not only derivatives that are stabilized with amino
groups on boron, but also those containing alkyl substituents
are readily deprotonated if bulky amides such as LiTMP
Scheme 11 or cyclopentadienides MCp (M = Li, Na) are used as the
BORON: ORGANOBORANES 13
X X
related compounds containing indenyl and fluorenyl groups
were reacted directly with group 4 amides to give group
(60) X = H 4 ansa-metallocene complexes.146 Moreover, silylated and
Fe B X (61) X = F
OC stannylated cyclopentadienylboranes (69) serve as efficient
OC reagents in reactions with transition-metal halides.147149
X X 2
NR2
B R2B ER3
[CpRFe(CO)2]
MesBBr2 (OC)2FeCpR B E = Si, Sn
Br
(68) (69)
Na[BAr F 4]
1. 5 equiv.
ArF = 3,5-(CF3)2C6H3 [CpFe(CO)2] It is interesting to note that boron may also be -
CpR = C5Me5 2. hn bonded to cyclopentadienyl groups. The decamethylboroce-
nium cation [Cp 2 B]+ [AlCl4 ] (70) was studied by X-ray
crystallography.150 Compound (70) features one 5 -bonded
and one 1 -bonded Cp ring, both of which are essen-
+
Me5 tially planar within the experimental error. The latter is
localized and shows a strong bond alternation with aver-
age C C and C C bond distances of 1.339(5) A and
Fe B 1.476(6) A, respectively. The different geometry in com-
OC OC B
OC Fe Fe parison to the ferrocene-like structure of the isovalent
C CO decamethylaluminocenium cation (Cp 2 Al+ ) was attributed to
[BAr F4] O the higher electronegativity of boron and a stronger and more
covalent BC versus the AlC -bond. A related 5 -bonded
(62) (63)
organoboron transition-metal complex (71) was obtained from
reaction of C5 Me5 BCl2 with K2 [Fe(CO)4 ].151
Scheme 12
+ CO
BR2 CO
OC Fe
BR2 CO
B B
BR2
(64) (65) (66)
(70) (71)
base.143 The formation of the borylcyclopentadienides (67)
was confirmed by X-ray crystallography. The crystal structures Transition-Metal Complexes of Cyclopentadienylboranes.
reveal a strong -interaction between the Cp ring and the boron The rich coordination chemistry of boryl and borate substituted
atom if alkyl groups are attached to boron. Borylindenides and cyclopentadienyl ligands has very recently been reviewed.69
borylfluorenides were prepared through similar routes.144,145 Group 4 and group 8 complexes have over the years been
studied most thoroughly and selected examples of their
chemistry and applications will be shown. The interested
BR2 BR2 reader is referred to the review by Aldridge for a more detailed
coverage that also includes various complexes of groups 5 7
and group 9.69
(67)
1. Group 4 Complexes. Borylated group 4 complexes have
been primarily investigated with regard to their utility as single
In many cases, deprotonation of the cyclopentadienyl- component olefin polymerization catalysts. The attachment of
boranes is not necessary in order to form transition- pendant boryl functionalities was envisioned to obviate the
metal complexes. For example, a large variety of need for external Lewis acid activation (see Section 7.3.3).152
bis(cyclopentadienyl)aminoboranes Cp2 B(NRR ) (68) and There are only a few cases of direct borylation of group 4
14 BORON: ORGANOBORANES
E = Sn E = Si
2ZrCl4 2ZrCl4(SMe2)2
B(C6F5)3
Zr
B(C6F5)2
F Cl Cl
+ (35) Ph
(72) Zr Ph B Zr B Zr
F F Cl Me2S Cl
H
F F
(76) (77)
(73)
(74) (75)
Cl SiMe3 X
Ti B N Ti
A structurally intriguing alternative design involves Cl X B iPr2N
SiMe3 N
the incorporation of the boron center into the bridge
of ansa-metallocenes.146,159 First efforts toward this end Ph
have been reported independently by Rufanov and Shapiro (78) (79)
(Scheme 13).149,160 Both groups took advantage of the
high selectivity of silicon and tin zirconium exchange
reactions, thus avoiding the need to deprotonate the
highly reactive bis(cyclopentadienyl)borane intermediate. Cl BCl2 Cl BCl2
Related boron-bridged indenyl complexes have been prepared Zr Zr
Cl PMe2 Cl PMe2
through similar routes.148,161 The boron-bridged zirconocene
(76) has been characterized by NMR spectroscopy, and
formation of the Lewis base complex (77) that contains (80)
BORON: ORGANOBORANES 15
Scheme 14
BX2 X2B BX2 BX2
M M M
and related multinuclear ferrocenyl assemblies as well as
BX2 for the incorporation of ferrocenylborane units into polymer
(81) (82) (83) structures.
R
B
X2B BX2 X2B BX2 M = Fe
M M M = Ru Me RBCl2
2 Fe Si Fe Fe
M = Os R = Ph, Cl
BX2 X2B BX2 Me
(84) (85)
ClMe2Si SiMe2Cl
(88)
(36)
Metalated ferrocenes also serve as convenient precursors
to ferrocenylboranes. Lithiated ferrocenes have been utilized
for the preparation of ferrocenylboronates FcB(OR)2 and The structural features and spectroscopic properties
1,1 -fc(B(OR)2 )2 and are especially suitable in the presence of ferrocenylboranes are highly intriguing, especially the
of ortho-directing donor-substituents.69 The borylation of interaction of the electron-rich iron atom with strongly Lewis-
disilylated ferrocenes with excess BCl3 on the other hand was acidic boron-substituents, which is evident from a tilting
reported to yield varying amounts of 1,3-diborylated product of the BX2 group out of the Cp plane toward the iron center
(82; M = Fe, X = Cl) in addition to the 1,1 -diborylated (Figure 2). The bending of the individual boryl groups has been
species (83; M = Fe, X = Cl).170 In contrast, when 1,1 -
distannylated ferrocenes were treated with equimolar amounts C33 C32
of boron halides, 1-stannyl-2-borylferrocenes (86) were C31 Br3
formed as the major product rather than the expected B2
1-stannyl-1 -borylferrocenes (Scheme 14).171 The 1-stannyl-
C34 C35
2-borylferrocenes thus obtained underwent further thermal
rearrangement to give heteronuclear bidentate Lewis acids
(87). Interestingly, the boron-bound chloride substituent in Fe2
(87) forms a bridge to the tin center, which consequently adopts Br4
an pseudotrigonal bipyramidal geometry as confirmed by X-
ray crystallography and multinuclear NMR spectroscopy.
While only trace amounts of 1,1 -disubstituted prod- C43 C42
ucts were observed in reactions of boron halides with C41
1,1 -distannylferrocenes, ring-opening addition reactions of
boron halides with strained silicon- and tin-bridged [1]fer- C44
rocenophanes yielded 1-silyl-1 -boryl- and 1-stannyl-1 - C45
shown by X-ray crystallography to decrease with increasing these materials in the solid state has been confirmed in
number of boryl groups.167,169 Thus, the degree of iron boron some cases by single-crystal X-ray crystallography and
interaction correlates with the number of Lewis-acidic boryl in others by powder diffraction studies.178 However, in
groups attached to the Cp rings; this conclusion was further solution, equilibration and partial dissociation occurs at
supported by DFT calculations.172 The interactions between elevated temperature. Intriguingly, the polymers are intensely
the metal center and the boryl group increase in the order colored as a result of charge transfer interactions between
Fe < Ru < Os. the electron-rich iron center and the electron-poor borylated
Piers investigated ferrocenylboranes containing pentafluo- heterocycles.178 A number of related macrocycles such as (90)
rophenyl substituents as potential cocatalysts in Ziegler Natta have been reported.
polymerization.173,174 The bifunctional borane (83) (M = Fe,
X = C6 F5 ) was found to effect methide abstraction from
Cp2 ZrMe2 under mild conditions. However, significantly
reduced polymerization activity was observed with the R B
Fe
monoborylated species (81) (M = Fe, X = C6 F5 ). This effect Fe B N NRR
was rationalized by a stronger degree of interaction with the R
n
electron-rich iron center, which lowers the Lewis acidity of (91) (92)
the boron center.
Borylated ferrocenes have been exploited by Wagner
as building blocks for the assembly of macrocycles and The first boron-bridged [1]ferrocenophane (91) was
coordination polymers (Scheme 15).175 Treatment of the discovered by Manners and Braunschweig.179,180 This highly
diborylated ferrocene 1,1 -fc(BMe2 )2 with the bifunctional strained organoborane shows a tilt-angle between the two
aromatic amines pyrazine and 4,4 -bipyridine, respectively, Cp rings of 35.2 , the largest reported thus far for a
led to spontaneous and reversible formation of (89) and related [1]ferrocenophane. As a result of the strain energy, the
ferrocenylborane polymers.176,177 The polymeric nature of boracycle (91) readily underwent ring-opening reactions,
and low molecular weight polymer accompanied by cyclic
oligomers (92) (n = 2,3) formed upon thermolysis at
BMe2 180 200 C. The related diborata[1.1]ferrocenophane (93)
Fe + N N was obtained by Wagner through a different route involving
treatment of dilithioferrocene with the diborylated ferrocene
Me2B 1,1 -(fcBMe2 )2 in the presence of 12-crown-4.181 The diborate
Me (93) tightly binds one lithium counterion in the ferrocenophane
B cavity. Electrochemical studies suggest that the lithium ion is
n
Fe Me only released after oxidation of the ferrocenophane.
Me
N N B
Me [Li(12-crown-4)2]+
(89)
B
NMe2
4+ B
Fe Li Fe Fe
B NMe
2
N N B
Me Me
B B (93) (94)
N N
Fe Fe
The first dibora[2]ferrocenophane (94) was prepared from
N N 1,1 -dilithioferrocene and 1,2-dichlorobis(dimethylamino)di-
B B
Me Me borane. A dynamic process due to motion of the cyclopenta-
N N dienyl rings between staggered and eclipsed conformations
was revealed by low-temperature NMR spectroscopy.182
A number of 1,3-dibora[3]ferrocenophanes with BEB
(90)
bridges (95; E=O, S, Se, Te, NR) were reported.183
Moreover, Wagner used diborylated ferrocenes for the
Scheme 15 Coordination polymers and macrocycles from ferro- synthesis of doubly bridged switchable ansa-metallocenes
cenylboranes (96) and (97), in which the bridges are created and
BORON: ORGANOBORANES 17
NR2 R R H
B B B 0 C
Fe PPh2 Fe N N BPr2
E Fe
PPh2 N N
B B B H BPr2
NR2 R R (100)
(95) (96) (97)
0 C
Ph
C NR2
+ N 2 Ph C N X X X X
BR2 R2B BR2 B
Cp2Zr
N Ph n
C
(101) (102) (103)
B(C6F5)3 X = S, O, NR). Lithium , silicon , or tin boron exchange
provide facile access to the desired borylated species. On
(99)
the other hand siloles and stannoles (X = Si, Sn) with
organoboron substituents in the 3-position are conveniently
Scheme 16 prepared via organoboration reactions.52 Another new
18 BORON: ORGANOBORANES
Et Scheme 18
N Et Me N Me
Et B B B B
B Et Me
Et N Et N Me
N
4
6 BORON AS PART OF UNSATURATED ORGANIC
(104) (105) (106)
RINGS
Among organoboron rings with multiple boron centers the Although 9-borafluorenes may be regarded as benzan-
five-membered (117) and six-membered diboracycles (118 nulated borole derivatives, their chemistry and physical
and 119) and related benzannulated compounds are commonly properties are quite different from those of C4 Ph4 BPh. A
studied systems, and a variety of other di- and triboracycles convenient route to 9-borafluorenes involves reaction of 2,2 -
have also been developed.102 These unsaturated rings have dimercurated biphenyl with boron halides.102 The sterically
been investigated extensively as ligands to transition metals, encumbered 9-borafluorene (122; Ar = 4-t-BuC6 H4 ) was
which has led for example to the development of various recently synthesized by reaction of 2,6-(4-t-BuC6 H4 )2 C6 H3 Li
multidecker sandwich complexes.101,103 Many other cyclic with the borane source H2 BCl(Me2 S).203,204 This boraflu-
organoboranes containing additional heteroatoms other than orene shows bright yellow luminescence, but addition of
boron and carbon (i.e. N, O, S, etc.) and systems with B B pyridine leads to quenching of the fluorescence.203 In contrast,
bonds are also known, but will not be covered here. In the the tetraphenylborole is blue-colored with max = 570 nm
following sections some recent developments in the chemistry and forms a light yellow pyridine complex.120 The pyridine
and applications of borole (114), boratabenzene (115), and complex of (122) was studied by single-crystal X-ray crys-
borepin (116) species will be highlighted. tallography. A long boron nitrogen distance of 1.638(4) A
in comparison to other organoboron pyridine complexes
suggests formation of a weak adduct. Indeed, the colorless
R R
complex partially dissociates in hydrocarbon solvents to give
R bright yellow fluorescent solutions. Yamaguchi and Tamao
B B B
exploited the luminescent behavior of 9-borafluorenes for
the design of a fluorescent fluoride sensor.205 A perfluo-
B B B rinated analog has been studied as an activator for olefin
R R R polymerization.206
(117) (118) (119)
Bu2SnH2 BCl3 L MR M+
Sn SiMe3 B SiMe3 B B
SiMe3 Bu Bu Cl L R
(127) (128) (129) (130)
K ClB(NMe2)2 B(NMe2)2 LDA Li+
K
THF/NEt3
B
(131)
NMe2
(132)
Scheme 19
BORON: ORGANOBORANES 21
B
FcBBr2
B B B B Co Fe Co
(37)
H H
N N H N N H
(141)
(137) (138)
R NR2 R
B B B
Several main group derivatives of boratabenzene have
been synthesized through reaction of boratabenzene salts with
Cl Cl PMe3
the appropriate metal halides.214 For example, treatment of Zr X Zr Zr
[C5 H5 BMe]Li with group 14 electrophiles Me3 EX (E = Si, Cl Cl PMe3
Ge, Sn, Pb) led to 1 -bonded compounds (139) that are
fluxional in solution. In contrast, reaction with divalent group B B B
R NR2 R
14 halides ECl2 led to bent-sandwich structures such as the
6 -bonded complex (140).227 X = SiMe2, CH2CH2
(142) (143) (144)
B Me
1-chloroborepin derivative (145) is perfectly planar as shown The radical anion has been detected by EPR spectroscopy, but
by X-ray crystallography. However, theoretical calculations decomposes at room temperature with a half-life of only about
demonstrate borepin to be much less aromatic than the isoelec- 10 min. The borate salt [Cp 2 Co]+ [B(C6 F5 )4 ] was identified
tronic tropylium ion.238 Moreover, amino groups effectively as one of the decomposition products.
compete with the 6p electron delocalization within the ring A family of amorphous molecular materials with diver-
by forming a partial BN double bond. The barrier to rotation gently extended -conjugation (147) was reported by
about the BN bond of 1-(N -benzyl-N -methylamino)borepin Yamaguchi and Tamao.25,245 Compounds (147) form stable
was determined by NMR spectroscopy to be 18 kcal mol1 .239
amorphous glasses with high glass-transition temperatures,
DFT calculations suggest that steric hindrance in substituted
and are characterized by reversible cathodic reduction and rel-
borepins and attenuated aromatic character result in significant
atively large HOMO LUMO energy gaps. High-performance
nonplanarity of the seven-membered ring.240
blue- and blue-violet-emitting organic electroluminescent
Mes
7 SELECTED APPLICATIONS OF B R R = H, Me3Si, Ph
ORGANOBORANES Mes
Na/K
7.1 Organoboranes as Optical, Electronic and Device
Materials Mes Mes
B R B 2 R
With its vacant pz orbital, three-coordinate boron is Mes Mes
inherently electron-deficient and acts as a strong -
(146)
acceptor.241 In contrast to other strong -acceptors such
as the nitro group, however, three-coordinate boron is not
generally inductively electron withdrawing. Importantly, it Scheme 21
BORON: ORGANOBORANES 23
devices were developed using the boranes as hole blockers cyclic voltammetry in DMF (N ,N -dimethylformamide)
and various arylamines as emitters.246 revealed a significantly more anodic reduction potential for
(150) (E1 = 1.95 V vs. SCE) and (151) (E1 = 1.98 V vs.
standard calomel electrode (SCE)) relative to that reported
R by Kaim for the reduction of the para-substituted isomer
(148) with E1 = 1.55 V and E2 = 2.25 V versus SCE.
Rajca further studied the electrochemical and preparative
reduction of (150) (equation 38).247 Cyclic voltammetry
in THF indicated two reversible reduction waves at peak
potentials Ep = 2.02 V and Ep = 2.64 V. By comparison
with monofunctional arylboranes, the more anodic peak was
attributed to formation of dianionic species. Preparative
reduction with sodium metal in THF/2-MeTHF yielded
the triplet diradical species (152) according to ESR
spectroscopy results.
B Reduction of the diborylated naphthalene derivative (52)
was studied by Gabba, who found a reversible reduction
wave at 1.81 V (vs. SCE) by cyclic voltammetry. Moreover,
treatment of (52) with potassium in THF in the presence of 18-
crown-6 led to formation of a dark purple EPR-active solution,
the spectrum of which suggested coupling of the electron spin
R R = H, NMe2, OMe, CN, BuC6H4CC R of the free radical with two boron centers (equation 39). The
(147) presence of an intramolecular one-electron -bond in (153)
leads to a significant shortening of the boron boron distance
as suggested by DFT calculations.248
Kaim reported on the UV/vis/near-IR spectroelectrochem-
istry of radical anions and dianions formed from bisborylated Mes Mes
benzene (148) and biphenyl (149) (Scheme 22).130 The B Mes B Mes
.
negatively charged species exhibit intense long-wavelength Na+
Na
absorptions in the visible or near-infrared region resembling
THF/
the spectral features of the analogous isoelectronic triary- 2-Me-THF . Na+ (38)
lamine radical cations. The quinoidal resonance structures B Mes B Mes
play an important role in the reduced species as confirmed by Mes Mes
ab initio calculations.
Okada and Oda studied the electrochemical properties (150) (152)
of the meta-substituted derivative 1,3-bis(dimesitylboryl)ben- .
zene (150) and the trifunctional species 1,3,5-tris(dimesityl- Ph2B BPh2 Ph2B BPh2
boryl)benzene (1,3,5-C6 H3 (BMes2 )3 ; (151)).124 Interestingly,
K/THF (39)
18-crown-6
Mes Mes
n = 1 (148)
B B
n = 2 (149) (52) (153)
Mes Mes
n = 1, 2
If oligothiophenes are used as the bridge between two
+ e e BMes2 units, amorphous luminescent materials (154) (n = 2)
and (155) (n = 3) with relatively high glass-transition
radical anion
temperatures are obtained. Both compounds undergo two
+ e e sequential reversible cathodic reductions, generating the
radical anion and dianion species. The oligothiophene
Mes Mes derivatives function not only as excellent electron-transporting
B B materials but also as efficient blue emitters with the most
Mes Mes intense fluorescence band at 440 and 488 nm for (154) and
n = 1, 2
(155), respectively.26,242 The bithiophene derivative (154) has
been successfully incorporated as a blue emitter into an organic
Scheme 22 light-emitting device.249
24 BORON: ORGANOBORANES
S Mes
MesBH2
Mes2B BMes2 n = 2 (154) Ar Ar B
n = 3 (155)
n
n
(158)
Bazan reported the synthesis, structure, and photophysical
behavior of a number of boratastilbene derivatives, which X
are highly emissive in the presence of donor solvents or Ar =
N
when crown ethers are added.250 Extended conjugation in the
bifunctional species (156) results in an absorption maximum
at 396 nm, which is red-shifted by 55 nm relative to that of the
monofunctional boratastilbene. The change in the absorption O(CH2)11CH3
and emission spectra upon addition of dibenzo-18-crown-6 Ar Ar = C6H2Me3
suggests a distinct effect of the counterions and of aggregation B Ar = C6H2(i-Pr)3
phenomena on the photophysical properties of these species.
O(CH2)11CH3 n
B (159)
B
Na+
(156) Na+ R R
ArB(OMe)2 Ar
Br Br B
A series of multifunctional anthrylboranes with up to 2 Mg
six boron centers and divergently extended -conjugation
R R
have been reported. Trianthrylborane itself is bright orange, n
whereas the extended system (157) is dark red colored.25 R = O(CH2)7CH3, O(CH2)11CH3 (160)
This bathochromic shift was attributed to the more extended Ar = C6H2Me3; C6H2(i-Pr)3
delocalization in the starbust oligomer (157). Two reversible
reduction waves were found for the two different boron
environments in (157). The anthrylboranes have also been Scheme 23
studied as fluorescent fluoride sensors (see Section 7.2.1).
conjugated organoboron polymers (158), that are related
to poly-p-phenylene vinylene (PPV) (Scheme 23).251 Bulky
mesityl or tripyl groups on boron prevent attack of
nucleophiles on boron and thus provide good stability
of these polymers. Interest in the incorporation of boron
into the main chain of conjugated organic polymers is
B B based on the expectation that extended delocalization may
be observed in a polymer consisting of electron-deficient
boron centers alternating with an organic -system. Despite
having relatively low molecular weight, the polymers are
B B highly luminescent with especially large Stokes shifts for
heteroaromatic polymers. An unusually large third-order
nonlinear optical susceptibility was also observed. Moreover,
recent electrical conductivity measurements on polymers
B B
with tripyl groups attached to boron and phenylene (or
fluorenylene) bridges showed an increase in conductivity
upon doping with triethylamine or iodine from less
than 1010 to ca. 108 106 S cm1 .252 Many other
vinyl, alkynyl, and arylborane polymers, all of which
(157) show strong fluorescence, have been synthesized. For
example, the polycondensation of lithiated diacetylenes with
In an elegant synthetic approach, Chujo used the aryldimethoxyboranes was used to produce poly(ethynylene-
hydroboration of bifunctional alkynes with boranes RBH2 phenylene-ethynylene-borane)s (159).253 The fluorescent
(R = 2,4,6-trimethylphenyl, Mes) for the synthesis of poly(p-phenyleneborane) polymers (160) were obtained
BORON: ORGANOBORANES 25
F
H
Me2B BMe2 Me2B BMe2
F
B B KH
F
(51)
(176)
Scheme 24 Schematic representation of selected bidentate hosts for
i-Pr anion binding
Ar = C6H4NPh2,
2-thienyl, 5-bithienyl [nBu4N]F
systems with aliphatic, olefinic, and aromatic backbones have
been developed and their chemistry has been reviewed.31,84,266
The diborylated cobaltocenium species [(CpBR2 )2 Co]+
MeO OMe (R = i-Pr) is an interesting example that illustrates the
different binding modes encountered for bifunctional Lewis
Ar B Ar acids.278,279 With hydroxy counterions, an oxygen-bridged
i-Pr
F complex (178), which represents an inverse chelate structure,
i-Pr was confirmed in the solid state and in solution (R = i-Pr,
F). Salt-like structures on the other hand were observed with
PF6 as the counterion and a zwitterionic 1:1 complex (179)
i-Pr
formed upon reaction of the diborylated cobaltocene with
hexachloroethane. Low-temperature NMR studies show that
Figure 4 Fluoride sensing with luminescent triarylboranes the chloride rapidly exchanges position between the two
Lewis-acidic boron centers.
N N
BR2 BR2 R2B
N Co Co Cl Co
O H
Cl
BR2 BR2 BR2
n
(178) (179)
Scheme 25 Scheme 26
BORON: ORGANOBORANES 29
(189) (191)
7.3.1 Achiral Organoboron Lewis Acids
F F
MeO
F B
Si Si SiMe2H + 12
F F 3 4
3
F F
(188)
F F
Diarylborinic acids (C6 F5 )2 BOH (189) and (3,5- B(C6F5)2
(CF3 )2 C6 H3 )2 BOH (190) were also studied as Lewis acid
(193)
catalysts. The borinic acid (189) adopts a trimeric struc-
ture in the solid state, but is monomeric in solution.294
These borinic acids are for example effective catalysts
for Mukaiyama aldol condensations and Oppenauer oxi- F F
dations, and the catalytic activities are typically much
higher than those of the corresponding arylboronic acids.16 B(C6F5)2
Nonetheless, 3,4,5-trifluorophenylboronic acid (191) and 3,5-
bis(trifluoromethyl)phenylboronic acid (192) were found to Si Si Si O F F
act as highly active amidation catalysts.295 Me Me
3 4
First attempts at developing supported versions of
(194)
perfluorinated arylboranes have recently been reported.28,296
Dendrimers containing a carbosilane core with up to 12
tris(perfluorophenylboryl) groups in the periphery have been Scheme 27
30 BORON: ORGANOBORANES
(198) (199)
B B
C6F5 C6F5 C6F5
O H F3C
C6F5
(195)
(41)
CF3
O
B
7.3.2 Chiral Organoboron Lewis Acids O
OH
Most chiral organoboron Lewis acids reported to date are
based on an organoborane that is attached to a chiral organic
moiety such as a diol, aminoalcohol, or other readily available
chiral substrates.14,17,19 Organoboron derivatives recently used (200)
as catalysts in enantioselective Diels Alder reactions include
the family of chiral acyloxyboranes (CAB) with (196) and
(197) as representative examples and various cyclic boronic elimination.17,19 It is thus difficult to recover them quantita-
esters such as (198) and (199). An interesting system that tively as alkylboronic acids. The chiral aryldichloroboranes
combines the favorable Lewis acid properties of fluorinated (202) are relatively more stable and can be reused as the
arylboranes with a chiral Brnsted acid has been developed corresponding boronic acid.301304 A bifunctional derivative
by Ishihara and Yamamoto.298,299 The Brnsted acid-assisted has recently also been synthesized from distannylated binaph-
chiral Lewis acids (BLA) (200) was found to be highly thyl through highly selective tin boron exchange.301 The
effective in enantioselective cycloadditions of ,-enals with binaphthylboranes (202) have been studied as catalysts for
various dienes. The presence of the Brnsted acid functionality enantioselective Diels Alder reactions involving cyclopenta-
leads to significant acceleration of the reaction. diene as the substrate.
R
OR O CO2H H
N O
O O
B R BCl2
B R R = H, Mes
O N BCl2
OR O Ts
R = alkyl R = alkyl R
(196) (197) (201) (202)
In contrast to the examples shown above, the organic Although several bifunctional chiral Lewis acids have
group itself is chiral in the alkylborane (201) and the binaph- been described in the literature and binding studies have
thyldichloroboranes (202). The naphthyl-functionalized been performed as outlined in Section 7.2, relatively little is
alkyldichloroborane (201) serves as an excellent catalyst in known about their use as Lewis acid catalysts. Most notably,
enantioselective Diels Alder reactions.300 The high selectiv- 1,8-bis(dichloroboryl)naphthalene was treated with various
ity was ascribed to a two-point binding process that involves chiral organic amines, alcohols, and acids. The resulting
an interaction of the substrate with the naphthyl group. While products were found to be efficient catalysts for asymmetric
chiral alkyldihaloboranes are among the most powerful chiral Diels Alder reactions.305,306 The simultaneous coordination
Lewis acids, in general they decompose relatively easily to of the substrate by both Lewis acid centers is believed to play
alkanes or alkenes as a result of protonolysis or -hydride a significant role (see also Scheme 25).
BORON: ORGANOBORANES 31
F C6F5 C F F C6F5 C F
6 5 6 5 [Ph3C]+ [B(C6F5)4]
F B F B
Ph3CMe
X
F B F B
Scheme 28
F C6F5 C6F5 F C6F5 C6F5
(209) (210)
1. KCN,
Et2O
2B(C6F5)3 [(C6F5)3B N C B(C6F5)3]
The perfluorinated diboraanthracene (211) shows an 2. Ph3CCl,
unusually high Lewis acidity as a result of the antiaromatic CH2Cl2 [Ph3C]+
nature of the central six-membered ring as described above (213)
for the monofunctional borane (206).37,123 The exocyclic
pentafluorophenyl groups are nearly perpendicular to the
(C6F5)3B N B(C6F5)3 (C6F5)3B N B(C6F5)3
N
diboracycle thus preventing any significant -electron density H2
from being transferred to the boron centers. The bifunctional
(214) (215)
species (211) is capable of coordinating a methyl group to
each Lewis acid center and shows very good catalytic activity
in combination with a number of transition-metal complexes. Scheme 29
Finally, a fluorinated 1,4-diborylbenzene derivative (212),
was studied as a nonchelating bifunctional activator in olefin bis(borane)s (214 and 215) have also been reported.316,317
polymerization. Use of (212) has been shown to result in Moreover, borane complexes of transition-metal cyanides
unusual polymer microstructures and has proven particularly such as [Ni(CN)4 ]2 provide access to anions with even
beneficial in copolymerizations.152 more extensive delocalization.317 Anion complexes of the
bidentate Lewis acids 1,2-C6 F4 (B(C6 F5 )2 )2 (210) function
F C6F5 F B(C6F5)2 on the same principle.313 All these counterions have been
F B F F F found to be highly effective in olefin polymerization. Finally,
borane or borate functionalities may also be directly attached
to transition-metal complexes as shown in Section 5.2, thus
F B F F F giving access to self-activating catalyst systems.146,154156,159
F C6F5 F B(C6F5)2
(211) (212)
8 RELATED ARTICLES
It is important to note that a large number of perfluorinated
tetraorganoborates that are for the most part directly related to
the tricoordinate species shown above have been prepared and Boron Hydrides; Boron: Inorganic Chemistry; Boron:
proven highly useful as activators in olefin polymerization. Metallacarbaboranes; Boron Nitrogen Compounds; Boron:
Usually either trityl, ammonium, or oxonium borates are Polyhedral Carboranes.; Hydroboration Catalysis.
reacted with a suitable transition-metal complex as shown
in Scheme 28.152 Borate salts may serve as highly active
cocatalysts since counterions BArF4 such as B(C6 F5 )4
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Acknowledgments
311. L. Li and T. J. Marks, Organometallics, 1998, 17, 3996.
312. L. Jia, X. Yang, C. Stern, and T. J. Marks, Organometallics, I am grateful to Ramez Boshra, Kshitij Parab, Yang Qin, and
1994, 13, 3755. Anand Sundararaman for their help with references.
Boron: Polyhedral H
H
H
H H
B B C C
Carboranes H
H
H
H
H H
H
B2H6 C2H6
Narayan S. Hosmane1 & John A. Maguire2 12 Valence electrons 14 Valence electrons
1
Northern Illinois University, DeKalb, IL, USA 14 Valence orbitals 14 Valence orbitals
2
Southern Methodist University, Dallas, TX, USA Electron-deficient Electron-precise
1 1 1
4
3 2 5 3 4 n=5
4
5 3 2 2 5
1
5 2 1
4 3 1
5 6 3 4 5 n=6
4
6 3 2 2 6
1
5 6 7 4 5 7
4 5 6 n=7
3 2 4 3 3 2
7 2 1 1 6
1
6 7 5 7
4 3 2 6
5
5 8 4 3 8 n=8
2 3 4
8
7 6 1 2 1
4 9 4
7 1 7 4 5 6
3
8 5 6 3 9 8 n=9
8 5 1 1 2 7
6 2
9 2 3
1
5 2
6 9 6 9
4 3
7 8 7 8
8 9 6 n = 10
5 10 5 10
7 2 3 4 2 3 4
10 1 1
1 11
10 9
2 3 9 11 6
5 6 8 7 7 8
n = 11
4 7 6 5 10
8 9 5 2 2 4
11 4 3 3
10 1 1
1 8 8
12 7 12 7
5 6 2 11 11
4 3 10 9 10 9 n = 12
10 11 6 2 6 2
7 5 3 5 3
9 8 4 4
12 1 1
Figure 2 Polyhedral atomic frameworks of idealized (a) closo, (b) nido, and (c) arachno carboranes showing conventional numbering
schemes. The lines drawn between cage atoms merely illustrate cluster connectivity, and should not necessarily be taken as bonds6
The structures of these compounds seem to dictate their a closed polyhedral structure. The closo carboranes, such
methods of preparation as well as their properties. The closo as C2 B4 H6 , C2 B8 H10 , C2 B10 H12 , and their C(cage) -substituted
carboranes are more thermally stable and less air sensitive derivatives, are also fairly stable to 250 C and above, and they
than the corresponding nido and arachno carboranes. This is often undergo thermally induced rearrangements that results
due to the fact that the nido and arachno carboranes lack in greater separation of the relatively negative carbon atoms
BORON: POLYHEDRAL CARBORANES 3
Structure types
via several diamond-square-diamond (DSD) processes.8 The as they have a high probability of preferentially localizing in
nido and arachno compounds, however, seem to generate tumor cells rather than normal tissues and are rapidly cleared
the corresponding closo carboranes at higher temperatures from normal tissues and blood, while being retained in tumor
indicating their thermal instability. Clearly, the structures of tissues. This results in high tumor to normal tissue ratios and
these carboranes seem to dictate their properties. high tumor to blood ratios. The research to date has shown
that BNCT has significantly prolonged the lifespan of patients
with deadly brain tumors. A number of carborane compounds
1.2 Practical Applications such as boronated organic species and boronated monoclonal
antibodies have been employed for this purpose.
The rapid development of carborane chemistry is mainly
due to their practical applications. For instance, the potential
utility of carborane polymers as gaskets, O-rings, and electrical Molecular Assemblies:11,12 Because of their rigid, ther-
connector inserts has been reported.1a Their functionality for mally and chemically stable three-dimensional structure, the
solvent extraction of radionuclides as well as the potential three icosahedral carborane isomers, commonly known as
medicinal value of the isoelectronic and isostructural boron o-, m-, and p-carborane (or 1,2-, 1,7-, and 1,12-C2 B10 H12 ,
analogues of biologically important molecules has been respectively), are being used as subunits for the assembly
the subject of many review articles.1,9,10 For example, a of larger arrays. The examples of such molecular assemblies
number of boron compounds have been found to possess include linear rigid rod-like molecules obtained by direct cou-
anti-inflammatory and antiarthritic activity in animal model pling of the carbon vertices of p-carborane, hybrid linear rods
studies. Boron compounds have also been implicated in studies by joining opposite boron vertices of p-carborane through
designed to probe the importance of the so-called anionic acetylene or diacetylene linkages, nonlinear oligomers of both
subsite of acetylcholine esterase and Ach receptors. But, by o- and m-carboranes, cycles of o- or m-carborane connected
far the most interesting practical applications of carboranes via their carbon or boron vertices through mercury atoms to
are in areas of boron neutron capture therapy (BNCT) and form novel mercuracarboranes, and carboracycles, which are
supramolecular assembly. cyclic compounds composed of o- and m-carboranes joined
through carbon vertices by a series of bifunctional organic
Carboranes in Boron Neutron Capture Therapy of Cancer linking groups of varying complexity. Thus, the development
(BNCT):9,10 The stable isotope of boron, 10 B (19.8% natural of the systematic synthetic routes toward nanometer-scale,
abundance), is very effective as a neutron capture agent structurally well-defined and rigid molecules has become a
with the effective nuclear cross section of 3837 barns, rapidly growing area of chemistry.
while the 11 B nucleus is incapable of undergoing a BNC
reaction. Therefore, the 10 B-enriched carborane and borane-
substituted biomolecules and drugs are selectively delivered
to the cancer cells in the human body and then the tumor- 2 RELATED ARTICLES
localized 10 B nucleii are bombarded with either thermal
or epithermal neutrons that results in a fission reaction Boron Hydrides; Boron: Inorganic Chemistry; Boron:
producing the high energy alpha () particles as shown in Metallacarbaboranes; Boron Nitrogen Compounds; Boron:
equation (2). Organoboranes.
10
5B + 10n 7
3 Li + 4 2 He + 2.7 MeV (2)
(c) A. K. Saxena, J. A. Maguire, and N. S. Hosmane, Chem. Acct. Chem. Res., 1976, 9, 446; (e) M. E. ONeil, K. Wade, in
Rev., 1997, 97, 2421; (d) V. I. Bregadze, Chem. Rev., 1992, Comprehensive Organometallic Chemistry I, eds. E. W. Abel,
92, 209; (e) R. N. Grimes, J. Chem. Educ., 2004, 81, 658; F. G. A. Stone, and G. Wilkinson, Pergamon Press, Oxford,
(f ) J. Plesek, Chem. Rev., 1992, 92, 269. 1982, Vol. 1, Chap. 1.
2. I. Shapiro, C. D. Good, and R. E. Williams, J. Am. Chem. Soc., 8. (a) W. N. Lipscomb and D. J. Britton, Chem. Phys., 1960, 33,
1962, 84, 3837. 275; (b) W. N. Lipscomb, Science, 1966, 153, 373.
3. I. Shapiro, B. Keilin, R. E. Williams, and C. D. Good, J. Am. 9. G. Rana, K. Vyakaranam, J. A. Maguire, and N. S. Hosmane, in
Chem. Soc., 1963, 85, 3167. Metallotherapeutic Drugs and Metal-Based Diagnostic Agents:
4. (a) T. L. Heying, J. W. Ager Jr, S. L. Clark, D. J. Mangold, The Use of Metals in Medicine, eds. M. Gielen, E. Tiekink,
H. L. Goldstein, M. Hillman, R. J. Polak, and J. W. John Wiley & Sons, 2004, Chap. 2.
Szymanski, Inorg. Chem., 1963, 2, 1089; (b) M. M. Fein, 10. (a) M. F. Hawthorne, Angew. Chem., Int. Ed. Engl., 1993, 32,
D. Grafstein, J. E. Paustian, J. Bobinski, B. E. Lichstein, 950; (b) A. H. Soloway, W. Tjarks, B. A. Barnum, F.-G. Rong,
N. Mayes, N. N. Schwartz, and M. S. Cohen, Inorg. Chem., R. F. Barth, I. M. Codogni, and J. G. Wilson, Chem. Rev., 1998,
1963, 2, 1115; (c) M. M. Fein, J. Bobinski, B. E. Lichstein, 98, 1515; (c) R. L. Rawls, Chem. Eng. News, 1999, 26.
N. Mayes, N. N. Schwartz, and M. S. Cohen, Inorg. Chem., 11. X. Yang, C. B. Knobler, Z. Zheng, and M. F. Hawthorne, J.
1963, 2, 1111. Am. Chem. Soc., 1994, 116, 7142, references therein.
5. (a) W. M. Maxwell, V. R. Miller, and R. N. Grimes, J. Am. 12. W. Jiang, I. T. Chizhevsky, M. D. Mortimer, W. Chen, C. B.
Chem. Soc., 1974, 96, 7116; (b) J. R. Pipal and R. N. Grimes, Knobler, S. E. Johnson, F. A. Gomez, and M. F. Hawthorne,
Inorg. Chem., 1979, 18, 263; (c) R. B. Maynard and Inorg. Chem., 1996, 35, 5417, references therein.
R. N. Grimes, J. Am. Chem. Soc., 1982, 104, 5983, and
references therein.
6. B. Stibr, Chem. Rev., 1992, 92, 225. Acknowledgments
7. (a) K. Wade, Adv. Inorg. Chem. Radiochem., 1976, 18, 1; We thank the National Science Foundation and the Robert
(b) R. E. Williams, Adv. Inorg. Chem. Radiochem., 1976, 18, A. Welch Foundation for their continuous support of authors
67; (c) T. P. Fehlner, C. E. Housecroft, in Molecular Structure research in the area of carboranes and metallacarboranes.
and Energetics, eds. J. F. Liebman and A. Greenberg, VCH,
Deerfield Fla, 1986, Vol. 1, Chap. 6, p. 149; (d) R. W. Rudolph,
Cadmium: Inorganic & 1 INTRODUCTION
Electronic configuration {Kr}4d10 5s2 Cd+ ionic radius (A) 1.14 (Pauling)
Atomic number 48 Cd2+ ionic radius (A) 0.97 (Pauling)
Atomic weight 112.411 1.03 (Goldschmidt)
Ionization potential (eV) Cd2+ hydration energy (kJ mol1 ) 1828
I 8.99 Hf (kJ mol1 )
II 16.90 Cd+ (g) 986.1
III 44.5 Cd2+ (g) 2623.5
IV 55 Cd2+ (aq., 1 M) 75.90
V 73 Gf (kJ mol1 )
VI 94
Cd2+ (aq., 1 M) 77.57
Electronegativity 1.69 (Pauling)
S (J K1 mol1 )
1.46 (Allred-Rochow)
1.4 (Mulliken) Cd2+ (aq., 1 M) 73.22
Atomic radius (A) 1.55
Covalent radius (A) 1.48
van der Waals radius (A) 1.58
Density (Kg m3 ) (c) 8642 (298 K) no amphoteric properties and, although cadmiate anions are
(l) 8010 (603 K) known, Cd does not dissolve in bases. With Zn and Hg (see
(l) 7930 (673 K) Zinc: Inorganic & Coordination Chemistry and Mercury:
(l) 7560 (973 K) Inorganic & Coordination Chemistry), Cd forms Group 12
Viscosity (mPa s) 1.44 (622 K), 1.18 (779 K), 1.10
(876 K) and has two s electrons outside filled d shells. Its usual
Specific heat (J g1 K1 ) 0.231 (298 K) oxidation state is +2, but also CdI species are known. Zn and
Hardness (Mohs) 2 Cd prove to be considerably more electropositive than their
Youngs modulus (GPa) 50 neighbors in the transition groups and no carbonyl, nitrosyl,
Sound velocity (m s1 ) 2310 alkene, and so on complexes of the type given by transition
Ohmic resistance (
m) 6.83 108 (293 K),
metal are known. However, their ability to form coordination
34.12 108 (773K)
Thermal conductivity 0.975 (273 K) polycrystalline compounds with ammonia, amines, cyanide (see Cyanides),
(W cm1 K1 ) and halide ions resembles that found for the d-group elements.
0.969 (298 K) polycrystalline Even though Cd chemistry closely resembles that of Zn, in
0.953 (373 K) polycrystalline some cases differences are still observed.2 Physical properties
Melting point (K) 593.9
of metal cadmium and Cd2+ ion are reported in Tables 1 and
Hfusion (kJ mol1 ) 6.067
Sfusion (J K1 mol1 ) 10.29 2, respectively.
Boiling point (K) 1038
Hvap (kJ mol1 ) 99.87
Svap (J K1 mol1 ) 95.98
Vapour pressure equation log(P/mm Hg) =
0.05223a/T + b 4 OCCURRENCE
liquid (773 1113 K) a = 99.90,
b = 7.897
solid (423 593 K) a = 109.00, The presence of Cd in the Earths crust is estimated to
b = 8.564 range between 0.15 and 0.11 g g1 (67th element in order of
C (J K1 mol1 ) 25.98 (c, ), 20.79 (g)
S (J K1 mol1 ) 51.76 (c)
abundance), with a Zn/Cd molar ratio about 450:1 (strongly
H f (kJ mol1 ) 0.59 (c, ), 0 (c, ), 112.01 (g) dependent on the nature of the rocks).3 Cd2+ ionic radius
G f (kJ mol1 ) 0.59 (c, ), 77.45 (g) (0.97 A) is similar to that of Ca2+ (0.99 A) and Na+ (0.98 A),
therefore Cd2+ is expected to be found substituting for Ca2+
and Na+ in their minerals. Moreover, Cd2+ shows high affinity
for calcite4 and iron oxyhydroxides surfaces. It reveals a
chalcophile nature and forms few minerals: the most important
Mg. In vapour phase, unstable Cd2 molecules have been are two sulfides, greenockite and hawleyite (hexagonal and
detected1 (bond energy about 7.4 KJ mol1 ). Cd exhibits a cubic form of CdS, respectively), a carbonate (otavite) and an
certain stability when exposed to dry air, but in the presence oxide (monteponite). Greenockite, in particular, is formed as
of moisture it is slowly covered with an oxide layer. It a yellow coating on weathering sphalerite (ZnS). Cd2+ gives
is softer and more malleable than Zn and can be easily isomorphous replacement in several Zn minerals, which can
laminated, extruded, drawn, and processed. A characteristic contain up to 0.5% of Cd. For this reason, sphalerite is the
sound (a sort of scream) is generated on bending a bar of the main industrial source of Cd. Under natural conditions, Cd
metal. Cd shows a great resistance to corrosion, a low-melting can be found in the atmosphere (0.1 to 5 ng m3 ) as a result of
point, and excellent electrical conduction. Unlike zinc, Cd has volcanic emission and release from vegetation.3
CADMIUM: INORGANIC & COORDINATION CHEMISTRY 3
Table 3 Main cadmium isotopes water hardness. Cd concentration in soil can reach high
levels,12 but high acidity increases the release of Cd2+ and,
Natural abundance (%) Emitter type Half-life consequently, its uptake by plants and bioaccumulation.3,11
+ In aquatic environment, invertebrates (most of all molluscs
97 3s
98 + 8s and crustaceans) accumulate Cd rapidly, followed by fish
99 + , 16 s and aquatic plants;13 as a matter of fact, sea organisms are
100 + , 1.1 min more resistant to Cd poisoning than those living in freshwater
101 + , 1.2 min
102 + , 6 min environment. Bioaccumulation in terrestrial plants results in
103 + , 7.5 min higher Cd level in animals involved in alimentary cycle
104 58 min of the plants; in some cases the presence of Cd in soil
105 + , 55.5 min inhibits the growth of some plants.3,11 Workers in Cd, Zn, and
106 1.22 stable Pb processing plants may be exposed to direct poisoning
107 + , 6.53 h
108 0.88 stable by Cd, but human uptake of Cd occurs mainly through
109 462 d food.3 Uncontaminated foodstuffs and cigarette smoke contain
110 12.39 stable low amount of Cd (see Nutritional Aspects of Metals &
111 12.75 stable Trace Elements) and drinking water normally does not show
112 24.07 stable significant metal content. Ingestion of Cd from contaminated
113 12.26 stable
114 28.86 stable foodstuffs gives rise to several diseases: in the case of that
115 , 59 h named itai-itai, Cd in the rice was found the etiological agent.
116 7.58 stable Cd is particularly absorbed by the respiratory tract: cigarette
117 , 170 min smokers may absorb 10 40% of inhaled Cd. Cd fume is an
118 50.3 min intense irritant and so pulmonary edema develops rapidly. In
119 , 2.96 min
120 50.8 s
the case of acute poisoning, the gastrointestinal tract absorbs
121 , 13.5 s only a small amount of Cd even though salivation, choking,
122 5.3 s nausea, vomiting, convulsion, and collapse may occur. Cd
123 2.09 s tends to accumulate in the liver and kidneys (about 50% of
124 , 1.24 s total body Cd). Metalothioneins (see Metallothioneins) found
in these two organs show high affinity for Cd2+ .14 These
metal-binding proteins act as sequestering agents, lowering
7 ISOTOPES Cd2+ concentration in critical tissue sites. The presence of
Cd2+ seems to induce the synthesis of the protein in the liver
Several isotopes (see Isotopes & Isotope Labeling) of Cd and kidneys. The half-life of Cd in the body is 10 30 years. Cd
are known,8 and 8 are stable (Table 3). For 111 Cd and 113 Cd, compounds show high oral toxicity, even though the emetic
the nuclear spin is 1/2 and they are used for NMR studies and irritant action is so violent that only a little Cd is absorbed
of Cd compounds and in biological fields (see Cadmium: so that fatal poisoning is rather uncommon.15 Cd compounds
Organometallic Chemistry). 113 Cd is used in the nuclear cause damage to kidney and to the central nervous system
industry because of its high neutron cross section. Unstable and are carcinogenic for connective tissue, lungs and liver
isotopes are prepared from nuclear reactions.9 Cd stable and, perhaps, teratogenic.15,16 Direct relationship between Cd
isotope composition in geological and meteorite samples has poisoning and thyroid dysfunction has been established.
been investigated using multiple collector inductively coupled
plasma mass spectrometry.10
9 SPECTROSCOPY
8 TOXICOLOGICAL AND ECOLOGICAL
INFORMATION 9.1 NMR Spectroscopy
111
Extraction and manufacture of Zn, Pb, and Cu ores can Cd and 113 Cd NMR spectroscopy has been used to
give pollution of the environment with Cd derivatives. Cd is study several complexes, both in solid state and in solution,
present also in industrial sludge and waste water. A source of and to investigate the binding site of the metal ion in
Cd release is the burning of fossil fuels and the incineration different metalloproteins.17 These isotopes have a spin 1/2
of rubbish. Fertilizers can contain variable amount of Cd. and, therefore, the broadening of the NMR signals due to
Toxicological characteristics and environmental fate3,11 of the quadrupolar contribution to NMR relaxation is avoided.
Cd resemble those of Pb and Hg (see Metal Ion Toxicity). The natural abundance is 12.75 and 12.26% for 111 Cd and
In aqueous environment Cd2+ shows a relative mobility: 113
Cd, respectively, but due to the lower receptivity of 111 Cd
it depends on pH, presence of organic molecules, and respect to 113 Cd, NMR investigations have mainly been
CADMIUM: INORGANIC & COORDINATION CHEMISTRY 5
performed with the latter isotope. 113 Cd chemical shift varies Cd complexes with glycine, alanine, and cysteine have
nearly linearly with concentration for cadmium perchlorate, been investigate using solid-state 113 Cd NMR spectroscopy
sulphate, and nitrate, while the halide salts show a large and the principal components of the 113 Cd shielding tensor
nonlinear relationship owing to the formation of mono- and determined. Cross polarization/magic angle spinning NMR
polyhalogeno complexes. Studies on a variety of organic and experiments have been used to calculate the principal
inorganic ligands bearing different donor atoms (see Donor elements of the 113 Cd shielding tensor for a collection of
Atom) revealed linear dependence on concentration and that: N-donor ligands. Composition and structure of a unusually
(i) ligands binding through the oxygen atom (sulphate, nitrate, highly charged [ClCd8 {SCH(CH2 CH2 )2 NHMe}16 ]15+ cation
nitrite, carboxylic acids, etc.) cause increased shielding of the have been determined by X-ray, XPS, and 113 Cd NMR
Cd nucleus; (ii) those binding through nitrogen (ammonia, measurements on microcrystalline powder.18 Solid-state 113 Cd
pyridine, azide, ethylenediamine, etc.) induce a marked NMR spectroscopy has been used to characterize a number of
deshielding; and (iii) ligands binding through the sulphur atom Cd thiocyanate complexes of varying stoichiometry.19 Several
(thiourea (see Thiourea), thiocyanate, etc.) cause a remarkable reviews have been published on metalloprotein studies.17,20
113
deshielding.17 Several Cd complexes with N-ligands (see Cd NMR spectroscopy has been successfully applied to
Ammonia & N-donor Ligands) show a line broadening, environmental studies.21
probably due to their slow dissociation rate in solution.
In many cases, binding constants of Cd complexes can be 9.2 Photoelectron and Vibrational Spectroscopy
calculated by the chemical shift or broadening. Extensive
investigations have been performed on Cd2+ -halide systems, Photoelectron spectra of Cd compounds have been
in aqueous and nonaqueous media, and the equilibria have reported (see Photoelectron Spectroscopy of Transition
been characterized.17 A somewhat surprising effect of halide Metal Systems), but discrepancies have been noted.2 X-ray
ions on 113 Cd NMR spectra in the presence of ATP as a photoelectron spectroscopy has been used in surface studies.22
function of pH can be observed: the Cd(ClO4 )2 ATP system Simmetry, bond length, and equilibrium constants (see
shows a downfield shift on increasing pH; the CdCl2 ATP Equilibrium Constant) of Cd complexes have been determined
system, however, shows an upfield shift. In the former case, through IR and Raman spectroscopy. Resonance Raman
the downfield shift may be due to the displacement of bound spectroscopy and Photoluminescence allow investigation of
H2 O, whilst in the latter the upfield shift is due to the the optical properties of ultrathin CdS films.23 Electron
displacement of coordinated Cl . Cd-substituted porphyrins, diffraction studies have been reported.24
in particular tetraphenylporphyrin (TPP), have been studied
using 111 Cd NMR and the 111 Cd15 N coupling constants
determined.17 Cd TPP adducts have been investigated by
111
Cd and 113 Cd NMR.17 The 113 Cd chemical shift observed 10 ELECTROCHEMISTRY
for aqueous Cd-EDTA is independent of pH between 4 and
11, but at pH > 13.8 gives evidence for the formation of
E and E1/2 values of Cd2+ /Cd couple and Cd complexes in
mixed hydroxo complexes. A large group of Cd compounds
aqueous solution have been measured through potentiometric
containing N-donor ligands have been investigated as a
and voltammetric methods (Table 4).25 Few data are available
function of counterion, chelate ring size, and basicity: in the
case of trisdiamine species, the deshielding effect decreases
in the order 4 5 6 7-membered chelate ring. The Table 4 Electrochemical data for Cd2+ in aqueous solvents
deshielding effect of anionic N-donors is much greater
than for neutral N-donors. 113 Cd113 Cd and 113 Cd111 Cd Standard potentials
Electrode E (V) vs. NHE
coupling constants have been determined for a number of
Cd2+ + 2e = Cd 0.4025
compounds containing multiple Cd centers.17 The trinuclear Cd2+ + 2e + Hg = Cd(Hg) 0.3515
anion (Na[Cd(SOPh)3 ]2 ) has been studied through 111 Cd Cd(OH)2 + 2e = Cd + 2OH 0.824
NMR spectra in Me2 CO and MeCN. In both the cases [Cd(CN)4 ]2 + 2e = Cd + 4CN 1.028
retention of bonding between Cd and S,O has been observed. [Cd(NH3 )4 ]2+ + 2e = Cd + 4 NH3 (aq) 0.613
Complexes with simple and N-protected amino acids have Half-wave Potentials (Hg electrode)
been investigated at different pH values. The results are Species Conditions E1/2 (V) vs. SCE
consistent with the presence of Cd complexes in which the Cd2+ NaClO4 , 0.1 M 0.59
ligand is bidentate, acting through N and O atoms. 113 Cd Cd2+ KNO3 , 0.1 M 0.58
NMR chemical shifts strongly depend on substituent effects [CdClx ]2x KCl, 0.1 M 0.60
in alkylcadmium compounds (see Cadmium: Organometallic [CdI4 ]2 KI, 0.1 M 0.65
[Cd(NH3 )4 ]2+ NH4 Cl, 1 M; NH3 , 1 M 0.81
Chemistry). Results have also been obtained by application
[Cd(CN)4 ]2 KNO3 , 0.1 M; KCN, 1 M 1.16
of magic angle spinning techniques to the 113 Cd NMR study [Cd(SCN)x ]2x KSCN, 2 M 0.664
of solid compounds, as powders, or as single crystals.2,17
6 CADMIUM: INORGANIC & COORDINATION CHEMISTRY
in nonaqueous media. The potential-pH diagram for Cd2+ /Cd (n = 1 4), but in presence of pyridine a white precipitate of
system has been determined and discussed in connection [Cd(py)2 (SCN)2 ] is observed.
with corrosion, immunity, and passivation.26 Cd can be
corroded at acidic and very alkaline pH values, but the
corrosion rate is fast only in the presence of oxidizing and
complexing agents due to the high hydrogen overpotential. In 12 ANALYTICAL METHODS
aqueous solution, Cd2+ gives a well-defined voltammetric
wave on Hg electrode, corresponding to a reversible, Cd2+ can be detected by the insolubility of its yellow sulfide
two-electron reduction.25 In the presence of complexing (see Analytical Chemistry of the Transition Elements).
agents (see Electrochemistry: Applications in Inorganic Several reaction and spot tests allow the identification of Cd2+ .
Chemistry), the E1/2 value shifts towards more negative Quantitative determinations are based on gravimetric (CdS or
values (Table 4): type and stability of the complex(es) -naphthylquinoline complex) or titrimetric (EDTA) methods.
can be often determined using DeFord-Hume or Shaap- Several physical techniques can be used in quantitative and
McMasters methods. In organic solvents, Cd2+ undergoes qualitative analysis: polarography (or related techniques, even
a single step bielectronic reduction; on Hg electrode it is in the presence of Zn, Cu, Bi and Pb), electrodeposition,
in most the cases reversible or quasi-reversible (Table 5). colorimetric methods, flamephotometric methods, neutron
activation, atomic absorption, and ICP spectrometry and ion
Cd2+ dodecyl sulphate micelles have been characterized
selective electrodes.
using voltammetric methods.27 CdS thin films can be
electrochemically obtained and pulsed sonoelectrochemical
synthesis of CdSe nanoparticles has been realized.28 Cd2+
sensitive electrodes are known. 13 STEREOCHEMISTRY
Coordination
number Compound {coordination core}
2 CdMe2 , CdX2 (gas phase, X = F, Cl, Br, I)
3 CdX3 (nonaqueous solvents, X = F, Cl, Br, I)
4 CdS2 {CdS4 }, CdCl2 (biuret)2 {CdCl2 O2 }, CdCl2 tu2 {CdCl2 S2 }, CdCl2 py2 {CdCl2 N2 }, CdCl2 (Ph3 P)2 {CdCl2 P2 },
Cd(HCO2 )2 tu2 {CdO2 S2 }
5 [Co(NH3 )6 ][CdCl5 ] {CdCl5 }, Cd(S2 CNEt2 )2 {CdS5 }, CdSO4 tu3 {CdS4 O}, Cd(thioglycollate)2{CdS4 O}, CdI2 (py
N-oxide) CdI3 O2
6 CdO {CdO6 }, [Cd(H2 O)6 ] {CdO6 }, Cd(acac)2 {CdO6 }, [Cd(imidazole)6 ](NO3 )2 {CdO6 }, [Cd(en)3 ]S2 O3 {CdN6 },
NH4 CdCl3 {CdCl6 }, RbCdBr3 {CdBr6 }, CdCl2 (urea)2 {CdCl4 O2 }, CdCl2 (imidazole) {CdCl5 N}, CdBr2 py2 {CdBr4 N2 },
Cd(NCS)2 {CdN2 S4 }, Cd(glycinate)2 H2 O {CdO4 N2 }, Cd(L-methioninate)2 {CdO4 N2 }, Cd(histidinate)2 {CdO2 N4 }
7 Cd(MeCO2 )2 2H2 O {CdO7 }, Cd(salicylate)2 2H2 O {CdO7 }, Cd(NO3 )2 py2 {CdO4 N2 }, Cd(NO2 )2 en {CdO4 N3 }
8 CdF2 {CdF8 }, Cd(NO3 )2 4H2 O {CdO8 }, Cd(maleate)2H2 O {CdO8 }, Cd(1,8-naphthpyridine)4(ClO4 )2 {CdN8 }
saccharinate anion), the cation [Cd(tea)2 ]2+ adopts a dimerizes to Cd2 2+ . This species is unstable and decomposes
monocapped trigonal prism (see Trigonal Prism) geometry in Cd and Cd2+ . Cd+ is oxidized to Cd2+ by alkyl and OH
and the seven coordination is achieved acting the former radicals. [CdL]+ (L = [14]ane-1,4,8,11-N4 ) was prepared by
tea ligand as tetradentate (see Tetradentate Ligand) and the pulse radiolysis (see Pulse Radiolysis).2 Cd+ and Cd2 2+
latter as tridentate (see Tridentate Ligand). A monocapped species have been identified using 113 Cd NMR relaxation
trigonal prism (see Trigonal Prism) geometry is found also measurements by adding Cd to CdI2 .2
in [Cd4 (TCPM)2 (DMF)4 ]4DMF4H2 O (TCPM = tetrakis(4-
carboxyphenyl)methane) that contains a tetranuclear Cd-
carboxylate cluster (see Cluster).31 Eight coordination is 14.2 CdII Compounds
rare. CdF2 contains a CdF8 core in a fluorite structure.
In Cd(NO)3 4H2 O, the four water molecules are square 14.2.1 Hydrides
planar (see Square Planar) and bidentate NO3 anions lie
above and below this plane. The structure of Cd(tea)2 (NO3 )2 Cd does not dissolve hydrogen in any significant quantities
(tea = triethanolamine) reveals eight-coordinated Cd2+ in a (see Hydride Complexes of the Transition Metals).35 CdH2
distorted hexagonal bipyramidal geometry. is quite unstable at room temperature, but its decomposition
8 CADMIUM: INORGANIC & COORDINATION CHEMISTRY
is slow below 253 K (see Hydrides: Solid State Transition and thionyl chloride; (ii) reaction between Cd(CH3 COO)2 and
Metal Complexes). It can be obtained in organic solvents as acetyl chloride in glacial acetic acid; (iii) reaction between
shown in equation (1) and (2): metal Cd and gaseous HCl at 450 C; (iv) reaction between
Cd(NO3 )2 4H2 O and concentrated HCl. CdBr2 and CdI2 may
LiAlH4 + 2CdR2 2CdH2 + LiAlR4 (1) be prepared by direct reaction of the elements.1 CdBr2 may also
2LiAlH4 + CdI2 CdH2 + 2AlH3 + 2LiI (2) be obtained by reaction between Cd(CH3 COO)2 and acetyl
bromide in glacial acetic acid. Oriented CdI2 crystals have
Gaseous CdH, CdD, CdH+ , and CdD+ are known, but not been prepared by reaction of gaseous HI with an Langmuir-
gaseous CdH2 .35 The Cd hydride complex Cs3 CdH5 has been Blodgett film of cadmium arachidate. Doped cadmium halide
isolated and characterized.36 It can be synthesized by reaction crystals have been grown and characterized.39 CdCl2 , CdBr2 ,
of CsH2 with metal Cd at high temperature and pressure. A and CdI2 form auto-complexes in aqueous solution.
tetragonal Cs3 CoCl5 -type structure containing tetrahedral (see
Tetrahedral) CdH4 2 units has been proposed with a CdD
14.2.3 Pseudohalides
bond distance of 1.82 A. In several complexes, CdH bond
has been observed.37 White Cd(CN)2 is sparingly soluble in water, except in
the presence of CN ions, owing to the formation of soluble
14.2.2 Halides anionic complexes.1 On heating it darkens and decomposes at
about 200 C. Cd(CN)2 , like Zn(CN)2 , has a cubic anti-cuprite
All four halides (see Halides: Solid-state Chemistry) structure. Colorless cadmium thiocyanate is sparingly soluble
are known (Table 7).1 CdF2 has a fluorite structure and is in water, ethanol, and liquid ammonia. In the solid, Cd2+ is
more ionic than the other halides, which have a substantially surrounded by an N2 S4 octahedron. Cadmium thiocyanate
covalent nature (see Covalent Bonds) and a layer structure.38 polymers exhibit highly anisotropic physical properties.40
In fact, CdF2 shows higher melting and boiling points and Yellow Cd(N3 )2 is prepared by mixing solutions of Cd(NO3 )2
lower solubility. CdCl2 , CdBr2 , and the form of CdI2 and NaN3 . The crystals are orthorhombic and decompose
consist of cubic close-packed halides with Cd2+ in octahedral with detonation when heated. Cadmium pseudohalides (see
sites between alternate pairs of layers. In the form of CdI2 , Pseudohalide) may be prepared by metathesis (equation 3).
however, the stacking of iodine layers follows the pattern
ABACAB.38 Unlike the other halides, CdF2 is not soluble CdSO4 + Ba(SCN)2 BaSO4 + Cd(SCN)2 (3)
in ethanol, ether, and anhydrous ammonia. CdF2 and CdI2
do not form hydrate (see Hydrates) while CdCl2 and CdBr2
can crystallize with 4, 2.5, or 1 and 4 or 1 water molecules,
respectively. On heating, these hydrate species (see Hydrates) 14.2.4 Oxides
generally change into basic halides. CdF2 may be prepared by
reaction between aqueous HF and CdCO3 . Several methods CdO is obtained by burning the metal in air or by pyrolysis
are known to obtain CdCl2 :1 (i) reaction between Cd(OH)2 of nitrates, carbonates, formate, or oxalate;1 the last two, in
Table 8 Physical properties of cadmium oxide, peroxide and Table 9 Physical properties of cadmium sulfide, selenide and
hydroxide telluride
been observed. In aqueous solution, the role of the complex such as a Cd2+ crown ether (see Crown Ethers)
hydration sphere in the equilibria involving CdX2 (X = Cl system.49 Stability constants of selected Cd2+ halide and
or Br) has been investigated through experimental and pseudohalide (see Pseudohalide) complexes are given in
theoretical methods: the results are consistent and suggest Table 10.
that CdX+ and CdX2 are strongly hydrated to form a
pseudooctahedral (see Octahedral) structure around Cd2+ ,
CdX3 is weakly hydrated, and CdX4 2 is almost fully 15.2 Oxygen Donor Ligands
unhydrated. In water, DMF, acetone, and ROH solvents,
Stability constants for Cd2+ oxygen ligand (see Ligand)
the anion donor strength follows the order I > Br > Cl .2
systems are reported in Table 11. Cd2+ in aqueous and
Stability constants of halide complexes in several solvents
solid Cd(ClO4 )2 6H2 O is coordinated by six water molecules
have been determined.48 A trigonally distorted CdBr6
(d = 2.31 A).2 The Cd2+ ion is easily hydrolyzed in water
octahedral (see Octahedral) structure characterizes Cs[CdBr3 ]
to give the equilibria shown in equations (4) and (5): the
in solid phase. Complexes of the type [CdX2 (C5 H4 NCOOR)n ]
former prevails when [Cd2+ ] < 0.1 M, the latter at higher
(n = 1, 2) may be obtained by reaction between esters of 2-
concentration.
pyridinecarboxylic acid and CdX2 (X = Cl, Br, I). In the case
of [CdI2 (C5 H4 NCOOR)2 ], Cd2+ shows a distorted octahedral
Cd2+ + H2 O CdOH+ + H+ (4)
(see Octahedral) structure with CdI2 N2 O2 coordination core.
+
In aqueous Cd2+ CN system, the species [Cd(CN)n ](2n) + H2 O +H
2+ 3+
2Cd Cd2 OH (5)
(n = 1 4) have been observed with no evidence for the
presence of species with n > 4. Stepwise complexation NMR and IR studies indicate that in water and methanol
pattern in liquid ammonia have been established by IR the covalency of the metal-oxygen bond varies in the order
and Raman spectroscopy. Cd(CN)2 2/3H2 Ot-BuOH with Hg < Cd < Zn. Several mixed Cd2+ hydroxide complexes
3D honeycomb-like [Cd(CN)2 ]n structure is obtained by are known. Multinuclear species containing Cd(-OH)M
recrystallization of cadmium cyanide (see Cyanides) in (M = Cd, Co or Cr) units have been structurally character-
aqueous ter-buthyl alcohol. On exposure to chloroform ized. In the case of [(bmnpaCd)2 (-OH)2 ](ClO4 )2 CH3 CN
vapour, the [Cd(CN)2 ]n framework undergoes a large- (bmnpa = N ,N -bis-2-(methylthio)ethyl-N -((6-neopenthyl-
scale reorganization and gives a diamond-like structure amino-2-pyridyl)methyl)amine), the reaction with CO2
with CHCl3 in the interstices. In water, the complexes gives a mixed carbonate complex: [(bmnpaCd)2 (-
[Cd(SCN)n (H2 O)x ](2n) (n = 1 4) have been detected but CO3 )2 ](ClO4 )2 CH3 CN. Cd(MeSO3 )2 2H2 O may be prepared
no polynuclear species. The solvent plays a certain role in the by reaction of CdCl2 and MeSO3 H in water. In Cd2 SO4 (OH)2 ,
binding ability of SCN : in [Cd(SCN)2 ] and [Cd(SCN)3 ] , Cd2+ lies in a highly distorted CdO6 environment, while a
the anion coordinates the metal ion through nitrogen in CdO7 core is found in Cd(BrO3 )2 2H2 O. Complexes of the
water and through sulfur in DMSO.2 [Cd2 (pn)2 (SCN)2 ] is type [Cd(H2 O)(6n) (SO4 )n ](22n) are observed in concentrated
polymeric with bridging SCN . In [Cd(en)2 (SCN)2 ] and aqueous solution of cadmium sulfate. In the crystalline struc-
[Cd(en)2 (SCN)Cl], SCN ion is monodentate via nitrogen, but ture (see Crystal Structures) of CdSO4 , a very distorted
the complexes have trans and cis octahedral (see Octahedral) CdO4 tetrahedron is found while solid Cd2 (NH4 )2 (SO4 )3 is
structure, respectively. High-resolution 113 Cd MAS NMR characterized by two nonequivalent Cd2+ octahedral (see
spectroscopy has been successfully used to investigate the Octahedral) sites. Templated linear and layered Cd2+ sulfate
structure of a variety of cadmium thiocyanate coordination complexes have been obtained by reaction between cad-
compounds in the solid state. The results indicate a correlation mium salts and H2 SO4 in the presence of organic amines. In
between CdN distances and values of the CdN indirect M[Cd(S2 O3 )2 ] (M = NH4 or Rb), the ligands (see Ligand)
spin-spin coupling constants.19 Unusual structures have been behave as bidentate (see Bidentate Ligand) through O and
observed in hybrid crystalline materials based on the anionic S. Cd2+ interacts with nitrite in aqueous solution to give
[Cd(SCN)3 ] polymeric complex and a cationic host-guest
Table 11 Stability constants for Cd2+ -O-donor ligand in water
2+
Table 10 Stability constants for Cd -halide (or pseudohalide)
systems in water Ligand logK1 logK2 logK3 logK4
Ligand logK1 logK2 logK3 logK4 SO4 2 0.71 0.13 0.48 0.02
S2 O3 2 2.08 1.74 1.66
F 1.15 0.41 0.98 NO2 1.82
Cl 1.77 0.80 0.64 0.2 NO3 0.04 0.05 0.9 1.3
Br 1.77 0.56 1.00 0.76 HCO2 1.04 0.19 0.52
I 1.96 1.33 1.15 1.44 MeCO2 1.08 0.61 0.40
CN 5.62 5.18 4.90 3.50 Malonate 1.63 0.73 1.04
SCN 1.16 0.33 0.14 0.02 Maleate 1.74 0.92
12 CADMIUM: INORGANIC & COORDINATION CHEMISTRY
[Cd(NO2 )n ](2n) (n = 1 4). For n = 1 or 2, nitrite acts as an of chloro-bridged Cd2+ in a CdCl3 O3 environment. Each pyri-
O-bidentate ligand but for n = 3 or 4, monodentate nitrite is doxine acts as a bidentate ligand through two oxygen donors
also found. In aqueous solutions of Cd(NO3 )2 spectroscopic and a third oxygen of the ligand bridges another Cd2+ . [CdI2 L]
measurements suggest the presence of [Cd(H2 O)5 (NO3 )]+ (L = pyridine N-oxide) has a trigonal bipyramidal (see Trigo-
ion.2 Solid trihydrate species contains an eight-coordinate nal Bipyramidal) structure characterized by infinite chains of
Cd2+ . Cd2+ nitrate coordination polymers of different [CdI] units alternately bridged through two I atoms and two O
dimensionality have been synthesized: [Cd(NO3 )2 (1,2-bis(4- atoms. In CdL3 Cl2 (L = OP(NH2 )3 ), Cd2+ is hexacoordinate
pyridyl)ethine)1.5 ]n has an infinite one-dimensional struc- and L acts as a N,O chelate. [Cd(O2 SR)2 L] (L = bipy or phen)
ture in which Cd2+ lies in a heptacoordinate environ- and [Cd(O2 SR)2 L2 ] (L = bipy or en) are pseudooctahedral;
ment, [Cd(NO3 )2 (1,4-bis(4-pyridoxy)benzene)1.5 ]n , however, sulfinate acts as bidentate in the former and monodentate in the
is characterized by a two-dimensional network in which Cd2+ latter. [Cd(NCS)2 (urea)2 ] shows Cd2+ in a distorted octahedral
has a pentagonal bipyramidal (see Pentagonal Bipyramid) configuration forming chains bridged by thiocyanate ions.2
geometry. In Cd(PO3 )2 and CdBa(PO3 )4 , Cd2+ is octahedral Bidentate acetate and six-coordinate Cd2+ ions have been
(see Octahedral). In Cd3 (P3 O9 )2 14H2 O the anion consists observed in [Cd(MeCO2 )2 (urea)2 ]. Synthesis and structure of
of discrete cyclic trimetaphosphate units; in each, Cd2+ is [Cd(3,3 -AZDB)2 ](H2 Nme2 )(NH4 ), a complex characterized
octahedrally surrounded by four phosphate oxygen and two by interpenetrating diamond networks, have been reported.53
water molecules. Layered cadmium-phosphonates have been Cd2+ lies in a height-coordinate environment with a tetragonal
obtained and their structure solved: in Cd(O3 PR)H2 O and antiprismatic geometry. In [Cd(acac)2 (bipy)], all the ligands
Cd(O3 PC2 H4 NH2 ) the layer arrangement is similar, the only are bidentate, while in [Cd(acac)(bipy)(H2 O)] water is also
difference being the replacement of the coordinated water coordinated to Cd2+ and acac acts as a monodentate. Both
molecule with the nitrogen atom of O3 PC2 H4 NH2 2 . For- the compounds show a distorted octahedral (see Octahe-
mate anion acts as a bridging ligand (see Bridging Ligand) dral) structure, more marked for the bipy adduct.2 Discrete
in Cd(HCO2 )2 and Cd(HCO2 )2 2H2 O; in the former, Cd2+ [Cd(acac)3 ] units have been identified in KCd(acac)3 H2 O, in
is seven-coordinate, but in the latter it is octahedral (see which Cd2+ is trigonal prismatic (see Trigonal Prism). A num-
Octahedral). Systems of the type Cd(HCO2 )2 M(HCO2 )x are ber of dimethylphosphine oxide complexes of cadmium with
well known.2 In Cd(MeCO2 )2 2H2 O, the acetate ions act halides have been obtained.50 The complex [CdL2 (THF)2 ]
as bridging ligands (see Bridging Ligand).50 The structure (HL = 2,6-t-Bu2 C6 H3 OH) shows an unusual square-planar
of [Cd(MeCO2 )2 (tu)] indicates Cd2+ six-coordinate by one Cd2+ structure, in which the metal ion is coordinated to
bidentate and two bridging bidentate acetate groups and by four oxygen atoms. This compound was isolated from THF
two bridging sulfur atoms of two thiourea (see Thiourea) (equation 6).
groups.50 A Cd2+ oxalate polymeric species Cd(C2 O4 )3H2 O
Cd[N(SiMe3 )2 ]2 + 2HL + 2THF [CdL2 (THF)2 ]
is obtained by slow decomposition of ascorbic acid in
presence of Cd2+ . The metal ion is found in a {CdO7 } + 2HN(SiMe3 )2 (6)
distorted pentagonal bipyramidal (see Pentagonal Bipyra-
mid) geometry due to five oxalate and two water oxygens. Cd2+ reacts with 3,5-di-t-buthyl-1,2-o-benzoquinine to
In cadmium cyanoacetate, Cd2+ lies in a NO5 octahedron.4 form a biradical compound which can add a neutral N-donor
[CdL2 (H2 O)n ]m (HL = phenylthioacetic acid) has a poly- ligand (py or bipy) to give 1:1 and 1:2 adducts.
meric structure with Cd2+ in an O5 S octahedron. A polymeric
structure with bridging oxalate groups has also been observed
in [Cd(C2 O4 )L2 ] (L = substituted pyridines or 4-toluidine). 15.3 Sulfur Donor Ligands
Cd2+ is found in seven-coordinate pentagonal bipyramidal
Selected stability constants for Cd2+ sulfur ligand
(see Pentagonal Bipyramid) O7 and O4 N3 environments
systems are reported in Table 12. Heterometallic ion
in [Cd(SalH)2 (H2 O)2 ]2 and [Cd(SalH)2 (py)3 ], respectively.50
[Mo3 CdS4 (H2 O)12 ]4+ may be obtained by reaction of
Other examples of seven-coordinate Cd2+ are known.2,51 Cad-
[Mo3 S4 (H2 O)9 ]4+ with Cd2+ in the presence of a reductant
mium maleate dihydrate contains both six and eight-coordinate
Cd2+ . Cd2+ succinate complexes of different dimension-
alities may be obtained employing organic amines.52 The Table 12 Stability constants for Cd2+ -S-donor ligand in water
Cd2+ citrate system in aqueous solution includes the species
[Cd(CitH2 )]+ , [Cd(CitH)], [Cd(Cit)] , and [Cd(Cit)2 ]4 .50 Ligand logK1 logK2 logK3 logK4
[Cd(CitH)(H2 O)]n crystallizes in the orthorhombic space 2-Thiourail 4.02 3.49
group and Cd2+ is octahedrally coordinated to citrate Thiourea 1.43 0.80 0.52 0.65
molecules and one water molecule. Citrate acts as a tri- N-Ethylthiourea 1.46 0.72 1.32 0.90
dentate ligand (see Tridentate Ligand) through the central and Dithiocarbaminoacetate 5.4 3.9 4.4
Thiosemicarbazide 2.7 1.7 1.6
one terminal carboxylate group and the alcoholic oxygen. The Ethyl thioacetate 1.27 0.85 0.39 0.21
complex [CdLCl2 ] (L = pyridoxine) consists of infinite chains
CADMIUM: INORGANIC & COORDINATION CHEMISTRY 13
or with metal Cd in p-toluenesulfonic acid aqueous solution. atoms. [Cd(tu)2 (MeCO2 )2 ] exhibits a CdS2 O4 arrangement.
Polymeric compounds of the type [Cd(RS)2 ]n are obtained N,N -diehtyl- and N,N -dimethylthiourea form 1:1 and 2:1
from electrochemical oxidation of Cd anodes in CH3 CN con- complexes. The 1:1 complex reveals a polymeric, halogen-
taining RSH or RSSR.2 In the polymeric cadmium thiolate of bridged structure with tetrahedral Cd2+ . Two types of 2:1
the type Cd(SC6 H4 R)2 , nature, and position of the substituent complexes have been isolated: one is monomeric with tetra-
R determine the dimensionality of the structure. In the case of hedral metal center; the other is polymeric, halogen-bridged
aliphatic thiolates, one, two, and three-dimensional structures with octahedral (see Octahedral) geometry. Cd2+ reacts with
have been observed. In catena-bis[-(N-methylpiperidinium- N ,N -dimethyl- and N ,N -dicyclohexyldithiooxamide (L) to
4-thiolate)] cadmium perchlorate dihydrate, each Cd2+ is give CdLX2 when X = Cl, Br, I or CdL2 X2 and CdL3 X2
found in a CdS4 environment, the structure is character- when X = ClO4 ; the former are nonelectrolytes, while the
ized by infinite chains of Cd2+ ions bridged by sulfur latter are electrolytes; in all the cases the ligand L is biden-
atoms.2 Polynuclear complexes (see Polynuclear Complexes) tate through S and N atoms and in CdLX2 the metal ion
are observed in a solution of Cd2+ and 3-(dimethylamino)- is octahedral with bridged halides.2 Cadmium bis(N ,N -
1-propanethiol (HL). In the pH range 3 11, the predomi- diethyl-monothiocarbamato) complex [Cd(OSCNEt2 )2 ]n is
nant species are [Cd(HL)4 ]2+ , [Cd3 (HL)6 ]6+ , [Cd3 (HL)8 ]6+ , polymeric and crystallizes in monoclinic group; Cd2+ lies
[Cd4 (HL)9 ]8+ , and [Cd4 (HL)10 ]8+ . Both mononuclear and in a distorted trigonal-prismatic geometry and interacts with
polynuclear species can be formed by ligand deprotona- two S,O-bidentate and two O-monodentate ligands (see
tion. Clusters (see Cluster) of the type [ECd8 (E Ph)16 ]2 Monodentate Ligand). A structure intermediate between
(E, E = S, Se, Te) have been identified using 113 Cd NMR. octahedral (see Octahedral) and trigonal prismatic (see
[ClCd8 {SCH(CH2 CH2 )2 N(H)Me}16 ](CLO4 )15 16H2 O exhibit Trigonal Prism) has been found for (Bu4 N)[CdL3 ] (HL =
an unusually high cationic charge and a peculiar structure.18 Et2 NCS2 H), where each dithiocarbamate (see Dithiocarba-
The thioacetate complex [Ph4 P][Cd(SC{O}CH3 )3 ] has been mate) chelates Cd2+ through two nonequivalent S atoms.
synthesized and the structure determined. Cd2+ is strongly Using an appropriate tetralkylammonium salt, complexes
bound to the sulfur atoms of three thioacetate anions and of the type (NR4 )[Cd(S2 CNEt2 )2 X] (R = Et, X = Cl, Br,
weakly to the corresponding oxygen atoms of the carbonyl SCN; R = n-Bu, X = I) have been prepared in acetone
groups. Thiocarboxylate complexes with 4,4 -bipyridine have by interaction between cadmium bis(dithiocarbamate) and
a polymeric structure.54 The complexes [Cd(HL)2 X2 ] (X = halides or pseudoahalides. In (Et4 N)[Cd(S2 CNEt2 )2 (SCN)],
Cl, Br, I), [Cd(HL)3 ](ClO4 )2 2H2 O and [CdL2 ] (HL = 4,6- Cd2+ shows a distorted trigonal-pyramidal geometry.
dimethyl-2(1H)-pyrimidinethione) have been synthesized.2 Bis(thiosemicarbazide)cadmium sulfate is polymeric with a
A polymeric structure with a bridged halogen characterizes sulfate-bridged structure in which the bidentate N,S-chelating
[Cd(HL)2 X2 ]. In (Et4 N)[CdL3 ] (HL = benzothiazole-2(3H )- thiosemicarbazide binds an octahedral Cd2+ . [Cd(thiazolidine-
thione) the ligand L is bidentate through N and S. 1,4,6- 2-thione)2 ] exhibits a polymeric structure in which the
trimethylpyrimidine-2-thione (L) and 1-methylpyrimidine-2- ligand is bidentate through N,S atoms. In [CdL2 L2 ] (HL =
thione (L ) form halogenated complexes with Cd2+ .51 In (EtO)2 PS2 H, L = hexamethylenetetramine), Cd2+ has a dis-
[CdL2 X2 ] (X = Cl, Br) and [CdL2 X2 ] (X = Br, I), the ligands torted octahedral geometry, but in (Me4 N)[CdL3 ] (HL =
act as bidentate through N,S atoms. [CdL2 Cl2 ] (L = 2- (i-PrO)2 PS2 H) a coordination intermediate between octa-
thiouracil) shows a pseudotetrahedral structure. In most of the hedral and trigonal prismatic (see Trigonal Prism) is
cases, a stronger binding ability of aromatic versus aliphatic found. Some Cd2+ complexes with crown thioethers (see
sulfur donor has been observed.51 Cd2+ in [Cd(thiooxinate)2 ] Crown Ethers) are known; in [(CdI2 )2 ([24]aneS8 )] two
is found in a distorted tetrahedral CdN2 S2 environment. Pseu- CdI2 units interact with the macrocycle (see Macrocy-
dooctahedral Cd2+ is observed in [Cd(ethylxantate)2 (phen)], cle). Each Cd2+ lies in a distorted trigonal bipyramidal
in which the ethylxantate is bidentate. In cadmium thiodiac- environment and is bound to three consecutive S atoms
etate hydrate the ligand is an O2 S donor and the metal ion of the macrocycle (see Macrocycle) and two I ions.
lies in a distorted octahedral geometry. In Cd(NH3 )3 S2 O3 In metallothioneins, sequences of the type Cys Y Cys
and 3Rb2 S2 O3 CdS2 O3 H2 O, the thiosulfate acts as a mon- are the primary binding sites for Cd2+ ; the structure and
odentate S-donor, but in Rb2 Cd(S2 O3 )2 it is bidentate. In properties of this kind of protein have been extensively
[Cd(CS3 )2 ]2 , the ligand binds as bidentate to give a four- investigated.55,56
membered chelate ring.2 In [Cd(tu)n ](ClO4 )2 (n = 4 or 6),
Cd2+ is bound through the S atom of the ligand. [Cd(tu)2 Cl2 ] 15.4 Nitrogen Donor Ligands
is monomeric with the metal ion in a tetrahedral CdCl2 S2
environment. In [Cd(tu)2 (HCO3 )2 ] and [Cd(Ettu)2 (NCS)2 ], Selected stability constants for Cd-nitrogen ligand systems
Cd2+ is six coordinated with infinite chains bridged by are reported in Table 13. [Cd(NH3 )2 X2 ] (X = Cl, Br) is poly-
sulfur ligands for the former and by the NCS ions for meric with Cd2+ octahedrally surrounded by two NH3 and four
the latter. In the monomeric [CdL2 Cl2 ], L (= pyridyl-2- bridged halogens. In [Cd(NH3 )6 ]X2 , however, [Cd(NH3 )6 ]2+
thiourea) binds through the pyridine nitrogen and thione sulfur octahedrons (dCdN = 2.37 A) characterize the structure.2 The
14 CADMIUM: INORGANIC & COORDINATION CHEMISTRY
Table 13 Stability constants for Cd2+ -N-donor ligand in water NH)2 ] and [CdBr2 (Ph3 P = NH)] structural units. In the aque-
ous Cd-en system, the prevailing species are [Cd(en)2 ]2+
Ligand logK1 logK2 logK3 logK4 logK5 and [Cd(en)3 ]2+ with tetrahedral and octahedral geome-
NH3 2.617 2.179 1.435 0.742 0.02 try, respectively. Complexes such as [Cd(en)][Pd(CN)4 ]
py 1.36 0.50 0.04 and [Cd(NH3 )2 ][Pd(CN)4 ] are able to form clathrate (see
bipy 4.22 3.58 2.60 Clathrate) compounds and may accept two guest molecules
phen 5.8 4.8 4.0 of phenol, thiophene or benzene.2 [Cd(en)(NO2 )2 ] is poly-
en 5.45 4.53 1.76
dien 8.4 5.4 meric with a seven-coordinate Cd2+ in pentagonal prismatic
trien 10.75 geometry. Ethylenediamine and cadmium halides yield poly-
Gly 4.14 3.46 2.14 meric complexes with bidentate bridging en; with Cd(CN)2 ,
-Ala 4.02 3.38 however, en gives 1:1 and 1:2 monomeric complexes, bind-
-Ala 2.88 2.65 ing the metal ion as a bidentate chelating ligand. The
His 5.39 4.27
Imidazole 2.70 2.40 1.60 0.95 0.60 polymeric [Cd(en)(NO3 )2 (4,4 -bipy)]n has a zigzag chain
structure bridged by bipyridine molecules. Cd2+ exhibits a
distorted N4 O2 octahedral geometry, being coordinated to
cation [Cd(NH3 )6 ]2+ is found to be the prevailing species in one 2 -en, two 4,4 -bipy, and two NO3 ions. The observed
aqueous solution of CdCl2 when the molar ratio NH3 /Cd2+ three-dimensional network is due to two kinds of NH O
is higher than 10. IR and Raman studies on [Cd(NH3 )4 ]2+ hydrogen bonds (see Hydrogen Bonding). A square pyrami-
and [Cd(NH3 )6 ]2+ indicate that the binding strength increases dal (see Square Pyramidal) five-coordinate Cd2+ has been
with decreasing the coordination number. The crystal structure found in [bis(2-dimethylaminoethyl)-methylamine] cadmium
(see Crystal Structures) of [Cd(NH3 )2 ][Ni(CN)4 ] shows two- thiocyanate: the amines and one of the thiocyanate ligand
dimensional polymeric sheets of [Ni(CN)4 ]2 anions bridged occupy the basal positions while the second thiocyanate is
by coordinating [Cd(NH3 )2 ]2+ ions. This unusual structural apical. 1:1 complexes are formed by interaction of Cd2+
arrangement allows clathration of small aromatic molecules with MeNH(CH2 )3 NH2 , dien, H2 N(CH2 )2 NH(CH2 )3 NH2 and
such as furan, pyrrole, pyridine, or thiophene, which inter- H2 N(CH2 )3 NH(CH2 )3 NH2 . Unusual compounds are formed
act via hydrogen bonds (see Hydrogen Bonding) with host with tripod-like tetramines: the crystal structure (see Crystal
lattice ammonias. Similar clathration ability is shown by Structures) of Cd2 (Me6 tren)I4 reveals the presence of a five-
[Cd(py)2 ][Ni(CN)4 ]. [Cd(H2 N(CH2 )8 NH2 )][Ni(CN)4 ]PhMe coordinate cation [CdI(Me6 tren)]+ with a slightly distorted
has a monoclinic structure in which toluene is found orien- trigonal bipyramidal (see Trigonal Bipyramidal) structure
tationally disordered within a rigid host cage. Cd2+ is found and of a dinuclear (see Dinuclear) anion [Cd2 I6 ]2 , formed
to be coordinated through the oxygen atom of HONH2 in from edge sharing between pairs of CdI4 tetrahedra.2 In
[Cd(HONH2 )2 X2 ] (X = Cl or Br) but through the N atom [Cd(Me6 tren)X2 ] (X = Cl, Br), Me6 tren acts as a terden-
of MeONH2 in [Cd(MeONH2 )2 X2 ] (X = Cl, Br, I). In aque- tate ligand and Cd2+ is five-coordinate. In [Cd(tren)Br]Br,
ous solution, [Cd(N3 )n ](2n) (n = 1 5) and the mixed species however, tren is tetradentate (see Tetradentate Ligand). A
[Cd(NO3 )(N3 )n ](1n) (n = 1 4) have been observed and the five-coordinate Cd2+ and tetradentate (see Tetradentate Lig-
stability constants calculated.2 Hydrazine in aqueous solu- and) amines are found in [Cd(H2 O)L](CIO4 )2 (L = Me6 tren
tion (80%) reacts with CdF2 to give (N2 H5 )2 (CdOF2 ) but or tren). In the corresponding anhydrous complex, a perchlo-
in anhydrous hydrazine CdF2 2N2 H4 and CdF2 3N2 H4 are rate ion substitutes the water molecule in the coordination
formed in which the presence of double and triple hydrazine sphere: [Cd(ClO4 )L](ClO4 ). Analogously, in the complex
bridges has been suggested. Cd(C2 O4 )(N2 H4 )0.5H2 O and [Cd(NO3 )L](NO3 ), a nitrate ion binds Cd2+ . The coordi-
Cd(C2 O4 )(N2 H4 )2 may be obtained by reaction between native properties of amino acids towards Cd2+ have been
CdC2 O4 and N2 H4 . In both the compounds hydrazine acts as extensively investigated.2 Type and stability of the com-
a bridging ligand (see Bridging Ligand), but oxalate is ionic plexes strongly depend on the structure of the amino acid.
in the former case and bidentate in the latter. N-acylhydrazine In absence of interacting side chain, the amino acid acts as
derivatives act as N,O-chelate ligands (see Chelating Ligands) a chelate ligand (see Chelating Ligands) through the amine
in complexes of the type [CdX2 L] (X = NCS, NO2 , NCO, nitrogen and the carboxylate oxygen. In [Cd(L Asn)2 ], Cd2+
1/2SO4 ; L = formyl-, benzoyl-, or nitrobenzoylhydrazine). is octahedrally coordinated in an O4 N2 environment and
[Cd(PhNH2 )X2 ] (X = Cl or Br) shows an octahedral Cd2+ the amide of the side chain results unbound. No evidence
environment, while in [Cd3 (PhNH2 )4 Cl6 ] two types of octa- for any interaction between the metal ion and the thioether
hedral sites have been observed: {CdCl6 } and {CdCl4 N2 }.2 In group is found in Cd2+ Met system. Two different structures
[CdCl2 (Ph3 P = NH)]2 , [CdI2 (Ph3 P = NH)2 ]2 2(CHCl3 ) and have been found to correspond to the formula Cd(Glu)H2 O.
[Cd2 Br4 (Ph3 P = NH)3 ] IR spectra indicate that Ph3 P = NH In the former case, Cd2+ has a distorted octahedral (see
acts as a N-donor. In the dimeric complexes the units are linked Octahedral) geometry and is coordinated by N(amino) and
by trans-halogen bridges, while [Cd2 Br4 (Ph3 P = NH)3 ] is O(-carboxylate) of one glutamate, by both the oxygen
polymeric with halogen atoms bridging [CdBr2 (Ph3 P = atoms side chain carboxylate of a second glutamate, by
CADMIUM: INORGANIC & COORDINATION CHEMISTRY 15
an -carboxylate oxygen of a third glutamate, and by a however, gives a tetrameric species [Cd4 F4 L12 ](BF4 )4 con-
water molecule. The latter case is better represented by the taining a Cd4 F4 cluster (see Cluster). [Cd(py)X2 ] (X = Cl,
formula Cd(Glu)(H2 O)Cd(Glu)(H2 O)2 H2 O; the glutamate Br) reveals a polymeric halogen-bridged structure in which
binds three Cd2+ ions and two different geometries for Cd2+ Cd2+ is coordinated by one pyridine, two bicoordinated, and
occur: one is a distorted pentagonal bipyramidal (see Pen- three tricoordinated halogens.51 Cadmium halides react with
tagonal Bipyramid), the other is a distorted square-based cyanopyridine to give 1:2 complexes; CdCl2 , alone, forms
trigonal-capped polyhedron. 13 C and 113 Cd NMR studies indi- a 1:1 complex with 2-cyanopyridine. The cyano-group does
cate Cd2+ unable to promote peptide nitrogen deprotonation not bind the metal ion. Cd2+ is octahedral (see Octahedral)
(see PeptideMetal Interactions). Surprisingly, Cd2+ sub- with halogen bridges in a 1:2 complex but tetrahedral in a
stitutes for nitrogen-bound hydrogen on RSO2 N-protected 1:1 species. A polymeric structure containing CdSCNCd
amino acids, especially in the presence of bipyridyl. In units is observed when 2- and 3-cyanopyridines react with
[CdX2 (acetamide)2 ] (X = Cl, Br, I or SCN), acetamide is Cd(SCN)2 to give a 1:2 compound.2 Even in this case, Cd2+ is
an N,O donor and halogens act as bridging ligands (see octahedral. In [Cd(HCO2 )2 L2 (H2 O)2 ] (L = nicotinamide) and
Bridging Ligand).2 In [CdCl2 (malonamide)2 ]MeOH, Cd2+ [Cd(MeCO2 )2 L2 (H2 O)2 ] (L = N,N-diethylnicotinamide), the
is octahedral (see Octahedral) and coordinated to biden- metal ion lies in an octahedral environment and is bound to
tate malonamides through N atoms. Complexes of the type the amide through the N atom. In the monomeric compounds
[CdX2 L2 ], formed by N-(2-pyridyl)acetamide (see Amide [CdL2 I2 ][CdLX2 ] (X = Cl, Br; L = bis(2-pyridyl)ketone), L
(Amido) Complexes), are octahedral and the amide binds acts as a bidentate N2 donor. [CdL(NO3 )2 (H2 O)]2 (NO3 )2
through the carbonyl oxygen and the heterocyciclic nitro- (L = adenine) is dimeric, Cd2+ lies in a N2 O6 environment
gen. In [CdL2 (SCN)2 ] and [CdL2 ](NO3 )2 (L = RCONHNH2 ; and is bridged by two water and two adenine molecules. In
R = Et, n-Pr, n-C5 H11 , n-C7 H15 ) L behaves as an N,O Na2 Cd3 (ATP)2 6H2 O, ATP binds through the nitrogen of the
bidentate ligand, but in [CdLn Cl2 ] (L = i-PrCH2 CONHNH2 ,
base and phosphate oxygens. Aqueous Cd(ATP)2 is pro-
n = 1 or 2) L binds only through an N atom. Cd2+ is
posed to be in dimeric form. Interactions between Cd2+ and
found in a distorted octahedral coordination in [CdL2 (SCN)2 ]
guanosine occur. Depending on pH, 1:1 complexes of the type
(L = PhCONHNH2 ) in which the hydrazide ligand acts as an
[CdL]+ and [Cd(HL)]2+ have been detected. The structure
N,O bidentate ligand and one thiocyanate ion binds through
of [CdL(H2 O)5 ]3H2 O (L = guanosine 5 -phosphate) shows
an S atom, but the other through an N atom.2 In Schiff
Cd2+ octahedrally coordinated by five water molecules and
base complexes obtained from 2-benzoylpyridine and ben-
the N-7 of the purine ring. 4,6-dimethylpyrimidine-2(1H)-
zoylhydrazine or salicylhydrazine, Cd2+ is coordinated by
thione (HL) forms the complexes [Cd(HL)2 X2 ] (X = Cl,
two N and one O atoms. The quinquedentate ligand 2,6-bis(2-
Br, I), [Cd(HL)3 ](ClO4 )2 2H2 O, [Cd(HL)2 (CF3 CO2 )2 ], and
methyl-2-benzothiazolinyl)pyridine reacts in basic conditions
as deprotonated ligand to give a five-coordinated complex of CdL2 . The ligand binds via S and N; in the chloride and
unusual structure.2 In tris(ethylenediamine)cadmium diben- bromide, the ligand seems to coordinate only through the
zohydroxamate, the metal ion lies in an octahedral (see N atom and bridging halides. In [CdL2 (H2 O)4 ] (L = 8-
Octahedral) N6 environment. A number of tetraacetate lig- azohypoxanthinate), Cd2+ is octahedrally bound to four water
ands bind Cd2+ . Structural aspects control the stability of molecules and two N-7of the purine anions. Flavoquinones
such complexes: the formation constant value for the 1:1 acts as a chelate via N and O atoms to give complexes of the
complex of ethylene-bis(N ,N -(2,6-dicarboxy)piperidine) is type [CdL3 ]2+ . In [Cd(bipy)2 (NO3 )2 ]1/2H2 O, Cd2+ is found
lower than that for EDTA due to the steric hindrance of the in two distinct N4 O2 octahedral environments, being the oxy-
piperidine ring. Dinuclear (see Dinuclear) species of the type gen donors and two nitrate ions in one case and one nitrate ion
[Cd2 L] have been observed when H4 L is ethylenedinitrilote- and one water molecule in the other. In [Cd(bipy)2 (SCN)2 ],
traacetic acid or 1,2-trans-cyclohexylenedinitrilotetraacetic Cd2+ has a N6 octahedral geometry. Studies have been per-
acid. [CdCl2 (imidazole)] has a polymeric structure in which formed on the interaction of Cd2+ with bipy in water and
octahedrally coordinated Cd2+ ions are bridged by two chlo- DMF.57
ride ions.2 [Cd(imidazole)3 ](SO4 )H2 O is also polymeric: the Bipyridyl-based molecules are used as bridging ligands
metal ion shows an octahedral (see Octahedral) geometry (see Bridging Ligand) to obtain a variety of network
due to three imidazole nitrogens, a water molecule, and two topologies and structural motifs starting from Cd(NO3 )2 .58
oxygens from sulfate. A number of species are observed {[Cd(4, 4 -bipy)2 ](NO3 )2 } gives a clathrate (see Clathrate)
in Cd2+ imidazole aqueous system: [CdL]2+ , [CdL2 ]2+ , complex by interaction with o-dibromobenzene and shows
[CdL3 ]2+ and [CdL(OH)]+ . Monomeric tetrahedral (see Tetra- catalytic properties towards cyanosilylation of aldehydes.
hedral) species [Cd(N-alkylimidazole)2 X2 ] (X = Cl, Br, I) or [Cd(2,4 -bipy)2 (NO3 )2 (H2 O)2 ] shows a distorted pentagonal
dimeric species have been synthesized. CdL2 F2 (L = 3,5- bipyramidal (see Pentagonal Bipyramid) geometry, being
dimethylpyrazole) is obtained by reaction between Cd(BF4 )2 Cd2+ coordinated by one monodentate and one bidentate
and L: the octahedrally coordinated Cd2+ ions are bridged NO3 , two water molecules and two 2,4 -bipy (both through 4-
by F ions to form a linear chain. 5-methylpyrazole (L ), pyridyl N atom).58 In [Cd2 (4,4 -bipy)2 (H2 O)3 (SO4 )2 ]3H2 O,
16 CADMIUM: INORGANIC & COORDINATION CHEMISTRY
the Cd2+ ions lies in two nonequivalent octahedral environ- and [Cd(diars)2 ](ClO4 )2 (see Arsine & As-donor Ligands).
ments and are connected by 4,4 -bipy molecules to form [Cd(diars)Cl2 ] is believed to have a polymeric octahedral
one-dimensional chains. Heptacoordinate Cd2+ is found structure.61
in [Cd2 (SO4 )2 (1,3-bis(4-pyridyl)propane)3 (H2 O)2.7 ]4.5H2 O
and [Cd2 (NO3 )4 (1,5-bis(4-pyridyl)pentane)3 (H2 O)].58 Tria-
15.6 Multinuclear Complexes
zole ligands such as 3,5-dialkyl-4-amino-1,2,4-triazole give
complexes with dimensionality from zero to three.59 In the
The anions [CoCdCl6 ]2 and [Co2 CdCl8 ]2 show an
phosphoraniminato complexes [CdX(NPEt3 )]4 (X = Cl, Br,
unusual structure: in the former, both the metal ions
I), a [Cd4 N4 ] heterocubane core is found. The Cd2+ ions
are tetrahedral and a CoCd bond is present;2 in
are bridged by N atoms of the phosphoranimidate ligands.
the latter, the tetrahedral (see Tetrahedral) Cd2+ is
Interactions between Cd2+ and macrocyclic ligands (see
connected by four bridging chlorides to two tetrahedral
Macrocyclic Ligands) bearing N and/or O donor atoms (see
Co2+ ions. The polynuclear complex (see Polynuclear
Donor Atom) (cyclic amines, ethers, porphyrin derivatives,
Complexes) [I2 Cd{(-NC)MnLx }2 ] (Lx = cis or trans-
etc.) have been extensively investigated:2,50,51,60 Interesting
(CO)2 {P(OR)3 }(dppm); R = Ph or Et, dppm = Ph2 PCH2 Ph2 )
spectroscopic and photochemical properties are shown by
is obtained by reaction between CdI2 and cis- or
several of these complexes. Generally, Cd2+ macrocycles (see
trans-[Mn(CN)(CO)2 {P(OR)3 }(dppm)], Cd2+ is tetrahedrally
Macrocycle) undergo metal exchange more easily than the cor-
coordinated to two I ions and two N atoms of bridged
responding Zn2+ compounds. Some cryptands (see Cryptands
CN ions. Complexes of the type [CoCd(SCN)4 Ln ] have
& Cryptates), however, reveal a remarkable selectivity for
a structure determined by the nature of the ligand L:
Cd2+ respect to Zn2+ and Ca2+ and thus could be used
when L = py or bipy, the compound is better formulated
in chelation therapy (see Chelation Therapy).2 The octaaza-
as [CoLn ][Cd(SCN)4 ] (n = 3 or 6), when L = phen, as
cryptand L = N(CH2 CH2 NHCH2 CH2 NHCH2 CH2 )3 N shows
[Co(phen)3 ][Cd(SCN)4 (phen)]. [NiCd(SCN)4 (THF)n ] (n = 2
a particularly high affinity for Cd2+ . In the cation [CdL]2+ ,
or 4) shows octahedral Cd2+ and Ni2+ for n = 4, but
the metal ion is eight-coordinated in a bicapped octahedral
only octahedral Ni2+ with bridging thiocyanate for n = 2.
geometry.
In [CoCd(SCN)4 (en)3 ], Co2+ is square planar (see Square
Planar). Cd[Mn(CO)5 ]2 forms a terpyridyl adduct with a very
15.5 Phosphorus and Arsenic Donor Ligands distorted trigonal bipyramidal (see Trigonal Bipyramidal)
structure. CdM(SCN)4 (M = Ni, Fe, Zn, Cu, or Co) reacts with
Cadmium halides react with phosphines to give com- a variety of N-donor ligands. Three type of complexes can
plexes of the type [CdX2 (R3 P)]2 and [CdX2 (R3 P)2 ].61 The be obtained: [Cd(SCN)4 ][ML6 ], polymeric CdM(SCN)4 2L
former are halogen-bridged dimers, the latter are tetra- or CdM(SCN)4 4L, and monomeric CdM(SCN)4 2L
hedral (see Tetrahedral). In [CdBr2 (Et3 P)]2 , Cd2+ lies in or CdM(SCN)4 4L. Tetranuclear [Cd2 Cu2 I4 L4 (DMSO)2 ],
a Br3 P environment with two bridged Br ions. In sev- pentanuclear [Cd2 Cu3 Br6 L4 (DMSO)2 ], and hexanuclear
eral solvents a monomer/dimer equilibrium occurs. [CdLI2 ] [Cd4 Cu2 Cl6 L6 (H2 O)] (HL = 2-dimethylaminoethanol) have
(L = P(CH2 SiMe3 )3 ) is monomeric in CHCl3 and the metal been prepared and the unusual structures determined.63
ion seems to be three-coordinated. Complexes with a Clathrates (see Clathrate) containing octahedral Cd2+ and
CdX2 /R3 P molar ratio of 2:3 are rare and of uncertain tetracyanonichelate (II) units have been synthesized and
structure and, as a matter of fact, they are not a mix- structurally characterized.64
ture of 1:1 and 1:2 compounds. [Cd(R3 P)(SCN)2 ] has a
polymeric trigonal bipyramidal (see Trigonal Bipyramidal)
structure, but [Cd(Ph3 P)(CF3 CO2 )2 ]2 is dimeric with two Cd2+
ions bridged by four carboxylate ligands. Complexes of the 16 RELATED ARTICLES
type [(phenoxide)2 CdLn ] (L = monotricyclohexylphosphine,
n = 1, L = Me3 P or n-Bu3 P, n = 1 and 2) are obtained
by reaction between Cd[N(SiMe3 )2 ]2 and the phe- Alloys; Analytical Chemistry of the Transition Elements;
nol in the presence of the phosphine.62 [(2,6-di-ter- Cadmium: Organometallic Chemistry; Mercury: Inorganic
butylphenoxide)2 Cd(monotricyclohexylphosphine)] has Cd2+ & Coordination Chemistry; Tin: Inorganic Chemistry; Zinc:
in a near trigonal planar geometry and a Cd-P bond Inorganic & Coordination Chemistry.
length of 2.5247 A. In the bis(phosphine) complex [(2,6-
di-ter-butylphenoxide)2 Cd(Pme3 )2 ], however, Cd2+ lies in
a distorted tetrahedral environment and the (average) Cd-P
bond length is 2.737 A. Adamantanoid cationic complexes 17 REFERENCES
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CADMIUM: INORGANIC & COORDINATION CHEMISTRY 17
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Cadmium: Organometallic less thermally stable and more light sensitive than the zinc
derivatives. As such, R2 Cd compounds should be stored
Chemistry cold and in the absence of light. A notable exception is
[(Me3 Si)3 C]2 Cd, which decomposes at ca. 300 C, and is also
stable to both air and water (as is the zinc analog).9
Niladri Narayan Gupta & David A. Atwood The lower thermal stability of R2 Cd compounds compared
University of Kentucky, Lexington, KY, USA with R2 Zn is undoubtedly a consequence of weaker CdC
bonds. The mean CdC bond dissociation energies (D)
Based in part on the article Cadmium: Organometallic Chemistry have been determined for some R2 Cd compounds, and are
by Gerard Parkin which appeared in the Encyclopedia of Inorganic intermediate between those of the Zn and Hg analogs, as
Chemistry, First Edition. summarized in Table 110 (see Bond Energies and Bonding
Energetics of Organometallic Compounds). The individual
1 Introduction 1 first and second bond dissociation energies have been
2 R2 Cd: Dihydrocarbylcadmium Compounds 1 calculated for Me2 Cd, demonstrating that the second bond
3 RCdX: Monoalkylcadmium Compounds 4 dissociation energy is substantially smaller than the first
4 Organocadmium Anions and Cations 6 [D1 = 234 6 kJ mol1 ; D2 = 64 10 kJ mol1 ].
5 Organocadmium Compounds in Organic and R2 Cd compounds have been studied by 113 Cd (12.3%
Organometallic Synthesis 6 abundance) NMR spectroscopy,1113 which indicates that the
6 Related Articles 8 113
Cd shielding increases irregularly in the order Me2 Cd < i-
7 References 8 Bu2 Cd < n-Bu2 Cd < n-Pr2 Cd < Et2 Cd < i-Pr2 Cd. Organo-
cadmium derivatives are also characterized by the observation
of 113 Cd-1 H coupling as satellites in the 1 H NMR spectrum
(Table 2).
The chemistry of organocadmium compounds is closely R2 Cd compounds were first obtained by the direct reaction
analogous to that of their zinc analogs, but is noticeably of cadmium metal with alkyl halides. Unfortunately, this
less well developed.1 Organocadmium reagents are in general method is limited and typically does not readily yield pure
mild and regioselective.2 Their principal importance is in products. However, the direct method is facilitated by the use
the preparation of ketones from RCOCl and (RCO)2 O. of highly activated cadmium slurries.1416
Organocadmium compounds have also been used for the The most general method of preparation of organocadmium
regioselective alkylation of quinones,3 although more recently derivatives involves the reactions of RLi, RMgX, or R3 Al with
organocadmium compounds have found use in MOCVD cadmium salts.17 For example, Me2 Cd is readily prepared
processes (see Metal Organic Chemical Vapor Deposition). by the reaction of Me3 Al with Cd(OAc)2 (equation 1),
Organometallic cadmium compounds, as with cadmium
compounds in general, are highly toxic.4 Specifically, Table 1 Mean bond dissociation energies for some R2 M (M = Zn,
mammals accumulate cadmium in the liver and kidneys. A Cd, Hg) compounds
number of review articles on organocadmium compounds and
D(MR) (kJ mol1 )
their uses are available.1,58
Zn Cd Hg
Me2 M 183 7 147 4 124 4
Et2 M 133 10 111 8 100 8
2 R2 Cd: DIHYDROCARBYLCADMIUM
COMPOUNDS
113
Table 2 Cd NMR data for some R2 Cd compounds
2.1 General Properties
113 Cd (ppm) 2
JCdH (Hz) 3
JCdH (Hz)
Dialkyl- and diarylcadmium derivatives are colorless Me2 Cd 0 52
compounds that are either liquids or low-melting solids. Et2 Cd 94 53 60
The compounds are noticeably more stable to air than the i-Pr2 Cd 207 56
corresponding zinc derivatives. For example, whereas Me2 Zn n-Pr2 Cd 46 50 55
n-Bu2 Cd 44 52
is pyrophoric, Me2 Cd only fumes in air. However, although the i-Bu2 Cd 22 50 70
cadmium derivatives are more air stable, they are substantially
2 CADMIUM: ORGANOMETALLIC CHEMISTRY
and (Me3 SiCH2 )2 Cd is obtained by (i) the reaction of by (i) the reaction of CdCl2 with C6 F5 Li (equation 9) and
Me3 SiCH2 Li with CdCl2 (equation 2),18 and (ii) the reaction (ii) the decarboxylation of (C6 F5 CO2 )2 Cd (equation 10).28
of Me3 SiCH2 MgCl with CdI2 (equation 3).19 An analogous
method has also been used to synthesize the silyl derivative Cd
(Me3 Si)2 Cd (equation 4).20 (Me3 Si)2 Cd is very unstable and (C6 F5 )2 TlBr (C6 F5 )2 Cd (8)
decomposes over 2 days at 20 C. CdCl2 + 2C6 F5 Li (C6 F5 )2 Cd + 2LiCl (9)
(C6 F5 CO2 )2 Cd (C6 F5 )2 Cd + 2CO2 (10)
2Me3 Al + 3Cd(OAc)2 3Me2 Cd + 2Al(OAc)3 (1)
2Me3 SiCH2 Li + CdCl2 (Me3 SiCH2 )2 Cd + 2LiCl (2)
A general synthesis of perfluoroalkyl derivatives (Rf )2 Cd
2Me3 SiCH2 MgCl + CdI2 (Me3 SiCH2 )2 Cd + 2MgClI (3) (Rf = CF3 , C2 F5 , n-C3 F7 , i-C3 F7 , n-C4 F9 , C6 F5 ) that
LiAl(SiMe3 )4 occurs in quantitative yield involves the reaction of
CdCl2 (Me3 Si)2 Cd (4)
perfluoroorganoiodides Rf I with a dialkylcadmium reagent
R2 Cd (R = Me, Et) in the presence of a Lewis base (see Lewis
It is also noteworthy that, in contrast to the synthesis of Acids & Bases), for example, glyme, diglyme, TMEDA,
R2 Zn compounds, R2 Cd derivatives are not readily accessible pyridine, or MeCN (equation 11).29 However, since the
by transmetalation (see Transmetalation) between R2 Hg and perfluoroalkylcadmium derivatives are strong Lewis acids
Cd metal, presumably since the electropositivity of Cd and Hg (see Lewis Acids & Bases), they are actually isolated as
is so similar that equilibrium mixtures are obtained. adducts, for example, (Rf )2 Cd(py)2 .
Cp2 Cd is obtained by reaction of Cd[N(SiMe3 )2 ]2
with CpH (equation 5).21 The orange red, light-sensitive 2Rf I + R2 Cd + 2L (Rf )2 CdL2 + 2RI (11)
pentamethylcyclopentadienyl analog Cp 2 Cd has also been
L2 = glyme, diglyme, (MeCN)2 , (py)2
prepared by the reaction between Cd(acac)2 and LiCp
(equation 6).22 It is worth noting that, in contrast, the analogous
reaction between CdCl2 and LiCp gives only colloidal
2.3 Structures of R2 Cd Compounds
cadmium and the organic dimer Cp 2 .23
Structural studies on simple R2 Cd compounds are rare.
Cd[N(SiMe3 )2 ]2 + 2CpH Cp2 Cd + 2HN(SiMe3 )2 (5) However, Me2 Cd is known to be linear with d(CdC) =
Cd(acac)2 + 2LiCp Cp 2 Cd + 2Li(acac) (6) 2.112(4) A in the gas phase on the basis of Raman studies,30
and [(CH2 = CHMe2 Si)(Me3 Si)2 C]2 Cd is linear in the solid
Perfluoroalkyl cadmium compounds are also known. state [CdC = 2.172(3) A] on the basis of X-ray diffraction
Bis(trifluoromethyl)cadmium has been prepared at 78 C (see Diffraction Methods in Inorganic Chemistry) as shown
by cocondensing Cd atoms with CF3 radicals generated in (1).31 The structure of Cp 2 Cd is not known, but an
in a hexafluoroethane plasma (see Metal Vapor Synthesis 1 , 5 -arrangement (see Hapticity) of Cp ligands (2) has
of Transition Metal Compounds),24,25 and also by the been proposed by analogy with that observed for Cp 2 Zn.
unusual reaction of activated cadmium powder with Similarly, on the basis of comparison with the zinc system,
difluorodihalomethanes, for example, CF2 Cl2 , CF2 Br2 , or Cp2 Cd has been proposed to be polymeric.32
CF2 BrCl, in DMF (equation 7).26
R2CdLn
CdX2 HX
[RCdX]n [RCdX]n
Ln
H2O H2O O2 O2
Cd(OH)2 [RCd(OH)]n R2Cd [RCd(OOR)]n [Cd(OOR)2]n
(6)
3 RCdX: MONOALKYLCADMIUM COMPOUNDS
(7) (8)
4(C6 F5 )2 Cd + 4H2 O [(C6 F5 )Cd(-OH)]4 + 4C6 F5 H (13)
investigated, confirming that the formation of EtCd(OR ) is Et2 Cd and O2 has also been studied and it has been claimed
more rapid than that for the bis(alkoxide) Cd(OR )2 .50 that an unusual adduct of composition Et2 Cd2O2 is formed
reversibly prior to formation of the alkylperoxo complex.57
R2 Cd + R OH RCd(OR ) + RH (14) Mixed alkylperoxide derivatives of the type MeCd(OO-
t-Bu) may be obtained by the reaction of Me2 Cd
The alkoxides [MeCd(OR)]4 (R = Me, Et, i-Pr, Ph) are with t-BuOOH (equation 16). Thermal decomposition of
tetrameric and are assumed to have cubic structures (11) MeCd(OO-t-Bu) gives an ill-defined product of composition
by analogy with the related zinc compounds. In contrast, [MeCdOC(O)HCdO].
the t-butoxy derivative [MeCd(O-t-Bu)]2 (12) has been
reported to be dimeric in benzene with the proposed structure Me2 Cd + t-BuOOH MeCd(OO-t-Bu) + CH4 (16)
shown, whereas the zinc analog is tetrameric. However,
methylcadmium alkoxides have also been studied by 113 Cd
NMR spectroscopy, which has suggested that the t-butoxy Me2 Cd reacts with H2 O2 to give a complex that is proposed
derivative may in fact also be tetrameric.51 to be the peroxy-bridged derivative MeCdOOCdMe, but was
not isolated (equation 17)
O2 O2
R2 Cd RCd(OOR) Cd(OOR)2 (15) Me
i-Pr
Cd S
i-Pr S Me
The mechanism of the reaction between Me2 Cd and O2 Cd Me Me t-Bu
has been investigated and a radical chain process has been Cd S Cd S
Me t-Bu
proposed (see Scheme 2). The initiation step is believed i-Pr i-Pr Me S Cd
to involve an ill-defined bimolecular reaction between two S Cd t-Bu
Me2 Cd molecules. The rate of initiation is inversely related Me Cd S Cd
S i-Pr
to O2 concentration, so it has been suggested that O2 can S Cd Cd S Me
i-Pr
also react competitively with the dimer. The reaction between Me Me t-Bu
(13a) (13b)
Me
2Me Cd Me Cd Me Cd Me
Dialkylcadmium compounds are also reactive towards H2 S.
Me
For example, (Me3 SiCH2 )2 Cd reacts immediately with H2 S to
O2 initiation
give CdS (equation 19).37 Other organocadmium compounds
Me2Cd + MeCdOOMe Me + Me2Cd + MeCd with CdS bonds include the thiocyanate derivatives RCdSCN
that are obtained by the reaction of R2 Cd with (SCN)2
Me + O2 MeOO (equation 20).58
propagation
MeOO + Me2Cd MeCdOOMe + Me
(Me3 SiCH2 )2 Cd + H2 S CdS + Me4 Si (19)
Scheme 2 Possible mechanism for the reactions of R2 Cd with O2 R2 Cd + (SCN)2 RCd(SCN) + RSCN (20)
6 CADMIUM: ORGANOMETALLIC CHEMISTRY
3.6 RCd(NR2 ) As such, anionic compounds of the types [R3 Cd] and
[R4 Cd]2 are typically not stable. However, incorporation
Alkylcadmium amide derivatives are rare. However, of electronegative substituents may stabilize such species. For
Cp 2 Cd reacts with Cd[N(SiMe3 )2 ]2 to give the amide example, (CF3 )2 Cd reacts with alkali metal halides (MX) in
bridged dimer {Cp Cd[-N(SiMe3 )2 ]}2 (equation 21).22 The polar solvents to give trifluoromethyl cadmate derivatives,
Cp ligands are bonded in an 1 arrangement as illustrated in for example, [(CF3 )2 CdX(DMSO)] (equation 24).41 Over
(14). a period of days, the samples are converted to the
species [(CF3 )3 Cd(L)] (L = DMSO, glyme, MeCN, py)
Cp 2 Cd + Cd[N(SiMe3 )2 ]2 [Cp Cd{-N(SiMe3 )2 }]2 (21)
and [(CF3 )4 Cd]2 , on the basis of 113 Cd and 19 F NMR
spectroscopy. For example, the 113 Cd NMR resonance of
the species [(CF3 )3 Cd(glyme)] is a dectet [2 J (113 Cd19 F) =
281 Hz] owing to coupling to three CF3 groups.
Me2 Cd reacts with Ga(P-t-Bu2 )3 to give the phos- Brightly colored (yellow to red) -arene compounds
phido derivative [MeCd(-P-t-Bu2 )]3 (equation 23).60 The (see Arene Complexes) of cadmium [(arene)Cd]2+ (e.g.
phosphido derivative is trimeric (15) and contains planar arene = C6 H6 , C6 Me6 ) have been obtained by the reactions of
three-coordinate cadmium centers. Cd(AsF6 )2 or Cd(SbF6 )2 with the arene in SO2 (equation 26).62
The structures of the compounds [(arene)Cd]2+ are not known
12Me2 Cd + 6Ga[P(t-Bu)2 ]3 4[MeCd{-P(t-Bu)2 }]3 with certainty.
+ 3[Me2 Ga{P(t-Bu)2 }]2 (23)
Cd(EF6 )2 + arene [(arene)Cd][EF6 ]2 (26)
2Ph3 P=CH2 + CdCl2 [Ph3 PCH2 CdCH2 PPh3 ][Cl]2 (27)
t-Bu
Me t-Bu
Cd P Other cationic compounds that have been isolated include
t-Bu ylide derivatives of the type [Ph3 PCH2 CdCH2 PPh3 ]2+
P Cd Me
t-Bu (equation 27).63
Cd P
Me t-Bu
t-Bu
(15) 5 ORGANOCADMIUM COMPOUNDS IN ORGANIC
AND ORGANOMETALLIC SYNTHESIS
and (RCO)2 O (equations 28 and 29). degenerate alkyl exchange reactions between Me2 Cd and
itself, and also between Me2 Cd and Men M (Men M = Me2 Zn,
R2 Cd Me3 Ga, or Me3 In), demonstrate that the exchange reactions
RCOCl RCOR (28)
occur via rapid bimolecular processes.68,69
R2 Cd
In some cases, alkylation may be accompanied by oxidation
(RCO)2 O RCOR (29)
of the metal center (equations 34 and 35).70,71
A common misconception concerned with the synthetic Me2 Cd + 2Cp 2 TiX 2Cp 2 Ti(Me)X + Cd (34)
applications of organocadmium derivatives is that they
R2 Cd + Cp2 V Cp2 VMe2 + Cd (35)
are unreactive towards aldehydes and ketones.17 This
misconception has arisen because the reactivity of an
organocadmium reagent depends markedly upon its method (CF3 )2 Cd has been used as a reagent to pre-
of preparation. Thus, in situ reagents, obtained by addition of pare other trifluoromethyl compounds, for example,
RMgX or RLi to a cadmium salt without further purification, (CF3 )3 Ga(DMF), (CF3 )3 In(MeCN)2 , and (CF3 )3 Tl(DMF)2
are reactive towards carbonyl derivatives (equation 30), (equations 36 38).72
whereas isolated pure R2 Cd compounds are inert. The
(CF3 )2 Cd
difference in reactivity between the pure and the in situ GaCl3 (CF3 )3 Ga(DMF) (36)
DMF
reagents may be traced to the presence of certain metal halides,
for example, MgI2 , which facilitate addition to the carbonyl (CF3 )2 Cd
group.65,66 Two possibilities for the function of the metal InCl3 (CF3 )3 In(MeCN)2 (37)
MeCN
halide include (i) activation of R2 Cd by forming a complex (CF3 )2 Cd
such as [R2 CdX2 Mg], or (ii) activation of the carbonyl group TlCl3 (CF3 )3 Tl(DMF)2 (38)
DMF
to nucleophilic attack by coordination to the oxygen atom
[R2 C=O MgX2 ]. 1
H and 19 F NMR studies of the reaction between (CF3 )2 Cd
1.R2 Cd/MgX2 and Me2 Zn have also demonstrated that ligand exchange
ArCHO ArC(H)(OH)R (30) occurs to give MeZn(CF3 ) and (CF3 )2 Zn.73 A summary of
2.H2 O
trifluoromethyl compounds that have been prepared from
In contrast to dialkylcadmium compounds, allylcadmium (CF3 )2 Cd is provided in Table 4.74
derivatives react readily with aldehydes and ketones in Fluorinated alkyl vinyl and aryl cadmium reagents can be
the absence of metal salts (equation 31).17,64 Substituted prepared in excellent yields just by stirring the fluorinated
allylic derivatives undergo rearrangement upon addition halides with activated cadmium metal.75 These reagents can
(equation 32). then be used to prepare the corresponding fluorinated stan-
nanes, which are versatile synthetic intermediate, by reacting
O them with tri-n-butyltin chloride at room temperature.76 Sim-
R R
ilar methods have been used to synthesize fluorinated copper
Cd + (31)
R R OH reagents.77
2
Heterocyclic derivatives of cadmium compounds can be
O
R3 R4
easily prepared by reacting the corresponding Grignard reagent
R1 Cd
+
R3 R4 OH
R2 Table 4 Trifluoromethyl compounds prepared from (CF3 )2 Cd74
2 R1 R2
(32)
Product Starting material
In a modification of the above procedure, the direct reaction P(CF3 )x I3x PI3
of cadmium powder with an allylic halide in the presence of Sn(CF3 )x Br4x SnBr4
an organic carbonyl gives homoallylic alcohols in good yield Ge(CF3 )x I4x GeI4
(equation 33).67 Me3 SnCF3 Me3 SnO2 CCF3
Me3 PbCF3 Me3 PbO2 CCF3
O Te(CF3 )4 Te(CF3 )2 Cl2
R1 X R3 R4 Sb(CF3 )3 SbCl3 , SbBr3 , SbI3
Cd/DMF
+ Bi(CF3 )3 BiCl3 , BiBr3
R3 R4 OH
R2 Ag[Ag(CF3 )4 ] AgNO3
R1 R2
(CF3 )2 Fe(CO)4 Fe(CO)4 X2 (X = Cl, Br, I)
(33)
CpCo(CO)(CF3 )2 CpCo(CO)I2
[Cu(CF3 )] CuCl
Dialkylcadmium derivatives readily partake in exchange (CF3 )2 M(PR3 )2 (M = Ni, Pd, Pt) MX2 (PR3 )2 (X = Br, I)
reactions with other metal compounds. NMR studies on the
8 CADMIUM: ORGANOMETALLIC CHEMISTRY
O O
R2 R6 R2 R6
(1) Et2Cd
(2) H2O
R3 R5 R3 R5
O Et OH
1 2
O O
R2 R6 R2 Et
(1) Et2Cd
R6
(2) H2O
O O
3 4
O O
R2 R6 R2
(1) Et2Cd
R5
(2) H2O
R3 R5 R3 Et
O O
1 5
Substrate Product
1a R2=R5=Me R3=R6=H 2a R2=R5=Me R3=R6=H (83%)
1b R2=R3=Me R5=R6=H 2b R2=R3=Me R5=R6=H (78%)
3 R2=R6=Me 4 R2=R6=Me (82%)
1c R2=R3=R5=Me R6=H 5a R2=R3=R5=Me (80%)
1d R2=R3=OMe R5=Me R6=H 5b R2=R3=OMe R5=Me (86%)
Scheme 3
10. W. V. Steele, Annual Report on the Progress of Chemistry, 38. M. J. Almond, M. P. Beer, M. G. B. Drew, and D. A. Rice, J.
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1.
Calcium-binding Proteins 1 INTRODUCTION
Receptor
Ca2+ Intracellular
ATPase
G
PLC Ptdlns(4,5)P2
Ca2+ CaBPs: Ca2+ buffer/transport
Ins(1,4,5)P3 Activation of enzymes
Polymerization of cytoskeleton
Cell-cycle progression
(Calmodulin,Ca2+ trigger)
IP3 receptor
Protein Ca2+
folding Ca2+ATPase
Metabolism
Endoplasmic
reticulum
Ca2+ Ca2+
CaBPs: Gene expression
Mitochondria
Cell membrane Apoptosis
Nucleus
Figure 1 Ca2+ signaling and Ca2+ binding proteins in a eukaryotic cell. (Reprinted from B.W. Schafer and C.W. Heizmann, Trends Biochem.
Sci., 1996, 21, 134. [ 1996, with permission from Elsevier])
Ca2+ circulation at alkaline pH and possession of a sequence studies of the elongation factor, aEF-1, from Methanobac-
domain similar to the eukaryotic Ca2+ -binding proteins, such terium thermoautotrophicum reveal that this protein binds
as calsequestrin (CSQ). ChaA homologues and proteins simi- calcium in the groove between helix 2 and strand 4. Cal-
lar to the eukaryotic Na+ /Ca2+ antiporter are widely present in cium may play either a structural role for protein stability or a
the bacterial world. Further, it has been reported that bacteria functional role in archaeal protein translation.28
contain Ca2+ -binding proteins are essential for cell adhesion, During the past few years, owing to the rapid progress
communication, and differentiation.1821 Some of the highly in genomic information and structural biological studies, our
conserved ABC transporters are regulated by Ca2+ with Ca2+ understanding of calcium-binding proteins has been greatly
binding proteins/domains and Ca2+ -dependent proteinase. expanded. Since 1991, the structures of calcium-binding
Additionally, previous investigations described CaM-like pro- proteins have been extended to more than 500 today and they
teins, such as calerythrin, with EF-hand Ca2+ -binding motifs are found in every cellular compartment. In this article, we
of helix-loop-helix in many bacteria.2224 Reddy et al. recently will first summarize the current knowledge about the common
reported that a calcium-binding protein CAMLP (calmodulin- properties of calcium-binding proteins. We then will highlight
like protein) was identified in Mycobacterium smegmatis.25 recent developments in structural biology and biological
Calcium-binding proteins have also been reported for functions of several classes of calcium-binding proteins.
archaea. A calmodulin-like protein with a molecular mass
of 24 kD was first found in an archaeon, Halobacterium sali-
narium. This protein is able to stimulate cyclic nucleotide
phosphodiesterase in a calcium-dependent manner and can
2 GENERAL PROPERTIES OF CALCIUM-BINDING
be suppressed by calmodulin inhibitors.26 In addition, the
PROTEINS
extremely heat-stable pullulanase from Pyrococcus woesei
binds two Ca2+ ions. Calcium plays essential roles in acti-
vation and stabilization of this protein against thermal and Calcium-binding sites are generally classified into three
guanidinium chloride-induced unfolding.27 NMR structural types.2931 Class I includes proteins whose Ca2+ binding
CALCIUM-BINDING PROTEINS 3
pockets are formed by a stretch of amino acids in the primary only 44 structures and 60 Ca2+ binding sites with a total
sequence (e.g. EF-hand proteins or -lactalbumin). EF-hand of 323 ligands from a total of 515 structures of Ca2+ -
proteins have a conserved motif of a Ca2+ -binding loop containing proteins. There was only one EF-hand site in this
flanked by two helices. All of the Ca2+ ligand residues of data set. Pidcock and colleagues have found that the average
-lactalbumin are composed of a 10-residue loop flanked by coordination number for Ca2+ was 6.0.30 Calcium-binding
two helices, C and D, plus two water molecules. This type sites of EF-hand proteins have a coordination number of 7,
of Ca2+ binding site does not belong to the EF-hand family which is consistent with previous findings.3640 The calcium-
owing to different ligand arrangements and the packing of binding sites in different classes of proteins can be identified
flanking helices (Figure 2). Class II sites have one ligand using the structural parameters by a computational program,
supplied by a part of the amino acid sequence far removed which is also further used for de novo design of calcium-
from the main binding sequence. D-galactose binding protein binding proteins.41 Among 162 calcium sites surveyed within
(GBP) belongs to this family. Several ligand residues in a the Cambridge Structural Database, an average of coordination
short loop with a Glu 63-residue apart form a calcium-binding number of 6.9 was found for small calcium chelators.30 A
pocket with the geometry very similar to that of EF-hand polydentate ligand with 3 6 oxygen atoms is able to form
proteins (Figure 2). Class III sites are created by amino acids calcium complexes with higher coordination numbers. The
remote from one another in the sequence. Proteins in this constraints of the backbone of proteins may be responsible for
group, such as cadherins, C2 domains, Site I of thermitase, the relatively low coordination number.
and Phospholipase A2 , have a Ca2+ binding site formed by A turn or loop structure was found to provide the bulk of
the ligand residues located remotely from one another in the the ligands to Ca2+ , but helix and sheet secondary structures
protein sequence. are slightly better providers of bidentate carboxylate ligation
Detailed analysis for the coordination properties of calcium than turn or loop structures. In the database analyzed by
versus magnesium in proteins and small molecules have been Pidcock and Moore, the relative populations of all protein-
carried out by Einspahr and Bugg,31 MacPhalen,29 Glusker,9 derived calcium ligand residues are 72.5, 13.4, and 13.5% for
and Natalie et al.36 in the past. An average coordination of turn/loop, helix, and sheet, respectively.30
7 for calcium-binding sites in proteins has been identified Table 1 shows the relative population of amino acids
for several databases containing the structures of calcium- used in the coordination for calcium binding. Asp has the
binding proteins. Recently, Pidcock and Moore have carried highest calcium-binding preference as revealed in the all CBP
out surveys of X-ray structures of Ca2+ - and Ln3+ -containing database by Pidcock and Moore30 and the EF-hand database
proteins and coordination complexes.30 To avoid biasing by Falke et al.42 The relative calcium ligand population
general conclusions concerning the coordination chemistry of is acidic residues > water > mainchain carbonyl > Asn >
protein-bound calcium, they selected a data set that contained Ser > Thr > Gln > Tyr. Carboxylate ligand residues of Asp
and Glu form the major class of calcium ligands from the
protein frame. It is interesting to note that Glu is a preferred
bidentate ligand for EF-hand proteins while Asp is commonly
used for non-EF-hand proteins.
To understand metal selectivity of proteins, Dudev et al.
have analyzed the first-second shell interactions in metal
binding sites in proteins.43 As shown in Figure 3, both
calcium and magnesium sites prefer carboxylates Asp and
Glu as metal ligand residues. On the other hand, magnesium
strongly prefers water in the first-shell coordination compared
to calcium sites in proteins. Peptide backbone groups were
found to be the most common second-shell ligand for
calcium-binding sites. The relative orders follow Asp/Glu
> Lys/Arg > Asn/Gln > Ser/Thr sidechains.43 Nayal and
Di Cera have found that the bond-strength contribution of
each ligating oxygen atom in the inner shell can be evaluated
(a) (b) (c)
by using an empirical expression successfully applied in
the analysis of crystals of metal oxides. The sum of such
contributions closely approximates the valence of the bound
Figure 2 Calcium-binding sites of (a) calmodulin, (b) -lactal- cation.44
bumin, and (c) thermitase are shown (top) and the pentagonal A detailed survey of 276 sequences of EF-hand proteins
bipyrimal geometry of calcium-binding sites in each protein is
enlarged (bottom). There are one, two, and zero water molecules has shown that 64% of the calcium-binding loops have four
in the enlarged binding geometries, respectively.3234 The structure acidic residues and 27% of the loops have three acidic
figures in this article are prepared using the program MOLSCRIPT35 residues at the ligand positions.45 Four acidic residues were
4 CALCIUM-BINDING PROTEINS
Percentage (%)
acid (%) (%) (%) 40
Asp 45 65 8
Glu 18 21 92 30
Asn 9.2 14 0
Ser 8.2 11 0
Thr 6.4 3.9 0 20
Phe 2.6 0 0
Lys 2.1 0 0
Gln 1.9 0.4 0 10
Gly 1.9 0 0
Tyr 1.5 0 0
Arg 0.79 0 0 0
Wa MC D/E N/Q S/T Y H K/R W
Cys 0.50 0.2 0 Ligand
Leu 0.32 0 0
Ile 0.32 0 0
Val 0.32 0 0 Figure 3 Percentage frequency distribution of the first-shell and the
Ala 0.24 0 0 second-shell ligands observed in the 3D structures of proteins bound
His 0.18 0 0 to Mg2+ - and Ca2+ -binding proteins. (Adapted with permission from
Met 0.15 0 0 Ref. 43. 2003 American Chemical Society)
Modified after Falke et al., 1994. Asp has the strongest calcium-
binding preference among all residue types. Glu is predominantly
used as a bidentate ligand. Carlo simulation.5053 Several other global factors, such as
hydrophobic properties and hydrogen-bonding networks have
been reported to contribute to calcium affinity.44,54,55 These
factors have less defined roles compared to the electrostatic
postulated to provide the most stable arrangement of anionic
interaction. They are likely to contribute to the dielectric
charges.46 Reducing or increasing the number of acid residues
environment that serves to shape the local electrostatic
at chelating positions will decrease the stability of the calcium-
field.42,44,47,54,55 Unfortunately, the estimation of the charge
binding complex.42,46 Electrostatic distribution outside of the
contribution to calcium affinity and selectivity in natural
coordination shell of the metal binding site has also been
calcium-binding proteins is complicated by the interference
shown to have a strong contribution to calcium binding.
of cooperative binding, calcium-dependent conformational
Charged side chains that are present on the surface of the
change, and electrostatic interaction between multiple calcium
proteins can exhibit strong influences on metal binding affinity
ions.9,3840
even if they are not directly involved as ligands.47,48 As shown
in Figure 4, the protein surface of calcium-binding protein
-lactalbumin is mostly negatively charged. In contrast, the
non-calcium-binding protein lysozyme has a highly positively
3 EF-HAND CALCIUM-BINDING PROTEINS
charged surface. The X-ray structure of bovine calbindinD9k
reveals a cluster of negatively charged amino acid sidechains
on the protein surface around the calcium sites. Linse and 3.1 EF-hand Calcium-binding Proteins: Overview
Forsen and their coworkers have shown that removal of
three negative surface charges Glu, Asp, and Glu at positions An EF-hand motif with a conserved continuous calcium-
17, 19, and 26 in the vicinity of the calcium-binding sites binding loop flanked by two helices (helix-loop-helix)29,37,42
of CBD (6.2, 6.4, and 11.1 A) leads to a 45-fold decrease was first described by Dr. Robert Kretsinger, who also
in average affinity (per site) at low ionic strength and a described the continuous calcium-binding loop in parvalbu-
five-fold reduction at 0.15 M KCl.49 The shifts in binding min (Parv).59 EF-hand calcium-binding proteins are found in
constants due to the reduction in affinity by the substitution prokaryotes to eukaryotes throughout the entire plant (Fungi
of Asp with Asn and Glu with Gln in seven surface included) and animal kingdoms. Rapid progress in genome
charge mutations have been accurately reproduced by Monte research demonstrates that the EF-hand motif is one of the
CALCIUM-BINDING PROTEINS 5
(a)
(b)
Figure 4 The electrostatic distributions of -lactalbumin (1ALC)56 (a) and chicken egg-white lysozyme (1LZ1)57 (b) calculated by Delphi
and presented by Grasp.58 Both surfaces of calcium-binding protein -lactalbumin are mostly negatively charged (a) (in red) while the surfaces
of noncalcium binding protein lysozyme (b) are mostly positively charged (in blue)
five most common protein motifs in human. Up to 600 entries conformation, which allows them to regulate target proteins.
in animal cells have been identified in all eukaryotes.59,60 Day The second manifests direct calcium-dependent enzymatic
et al. have identified a maximum of 250 putative EF-hand activities. Examples include aequorin, calcium-dependent
proteins in the plant Arabidopsis.61 According to the sequence protein kinase, calcineurin, calpain, and CaM domain protein
similarity, EF-hand proteins are classified into 77 distinct sub- kinase.68,69 The third type of proteins do not interact with other
families that contain two to twelve copies of the EF-hand. proteins but act as intracellular calcium buffers modulating the
These include CaM, Parv, troponin C (TnC), sarcoplasmic free cytosolic calcium levels and preventing cells from calcium
calcium-binding protein, the essential and regulatory light overload and apoptosis.70 Buffer proteins like CBD and Parv
chains of myosin, CBD, and the S100 and visinin or recoverin bind calcium without a significant change in the protein
(VIS) subfamilies.62 One of the 77 EF-hand subfamilies is conformation. The calcium affinities for EF-hand proteins
found in viruses and five are found in bacteria.62 vary by 106 -fold or more according to their biological roles.
Transient change of intracellular calcium concentration is Trigger proteins have affinities with Kd of 106 M. Parv has
sensed primarily by EF-hand calcium-binding proteins such the highest affinity of Kd (about 109 M). Calpain, on the
as calmodulin (CaM) and TnC located in the intracellu- other hand, has a Kd of mM.
lar environment.63 In addition to EF-hand proteins in the As shown in Figure 5, EF-hand motifs can be divided into
cytoplasm, this highly conserved EF-hand motif was also several major classes: canonical (classical), pseudo-EF-hand
found in other subcellular compartments and associates with motifs, essential light chain (ELC), and BM40.37,62 The canon-
membranes.6466 S100, a multigenic family of nonubiquitous ical EF-hand consists of -helix E (helix I, residues 9 to
calcium-modulated proteins of the EF-hand type expressed in 1), 12-residue calcium-binding EF-loop (1 12) and -helix
vertebrates exclusively, has been implicated in intracellular F (or Helix II, 10 20).62 The loop sequence positions 1 (x-
and extracellular regulatory activities.67 Although more anal- axis), 3(y), 5(z), 7(y), 9(x), 12(z) coordinate the calcium
ysis of other genomes such as Archaea and virus is needed, ion in a pentagonal bipyramidal geometry. The statistic data
given the important function of calcium signaling in cell shows that the side chain of Asp almost always (99%) serves
development and proliferation, it will not be surprising that as the ligand at position 1, and the glutamate side chain at
EF-hand proteins are found in all kingdoms and in every position 12 (z axis) binds in a bidentate mode to calcium
cellular environment. (92%).47 The x-axis (position 9) is filled by a bridged water
There are several major functional classes of EF-hand molecule connecting the side chain of aspartic acid, serine,
proteins. In the first class, trigger proteins like CaM or asparagine. The pseudo EF-hand motif has two additional
and TnC bind calcium with a large change in protein residues with mainchain carbonyl oxygen at positions 1, 4, 6,
6 CALCIUM-BINDING PROTEINS
Helix E Helix F
Canonic E n * * n n * * n x * y * z G -y I -x * * -z n * * n n * *
=O wa bi
E/Q
Pseudo * n * * n n * * n x * * y G z * * -y L -x K * -z n * * n n * *
=O =O =O =O wa bi
E/Q
ELC # n * * V F # L F D F W D G R D G * V D A n K n G D n n R C L
x -x -y
D/E E/D y z -z
=O =O =O
BM40 P n * W * n * * L x * H p * z * -y L -x * * -z n * P n * * P n
D y D =o wa bi
E/Q
Figure 5 The sequence patterns of four different types of EF-hand motifs. (Ref. 62. Reproduced by permission of Springer Verlag)
(b) (d)
intermolecular dimer with five mutated EF-hand motifs as important activities including recent advances in structural
seen in calpain.76 Almost all the members of S100 proteins information.
such as S100B, calcyclin, psoriasin, p11, as well as calpain
and neurocalcin form homodimer or heterodimers. It is clear
3.2.1 Calcium-induced Conformational Change of
that dimerization is one of the essential mechanisms that
Calmodulin
enable EF-hand proteins to effectively regulate multiple target
proteins. In the past few years, significant progresses have High-resolution methods, especially the newly developed
been achieved in structural analysis of EF-hand proteins both residual dipolar coupling (RDC) NMR in a dilute liquid
in apo- and holo-forms.76,77 crystalline phase (lipids or phage) have been shown to be
a powerful method for monitoring the structural properties
of calmodulin upon calcium binding.74,77,78,8587 As shown
3.2 Calmodulin
in Figure 6, in the apo-state, CaM is in a closed form and
Calmodulin (CaM) is a ubiquitous intracellular protein that the two flanking helices are in an antiparallel position.
mediates more than 100 different biological systems in both Calcium binding to the EF-loop results in the movement
calcium-free and -loaded forms. CaM has 148 amino acids of bidentate Glu at position 12 to form a better-defined
and its primary sequence is highly conserved in all cell types. calcium-binding pocket. Concurrently, this move of Glu 12
It shares strong sequence and structure homology to TnC, pulls residues of the attached helices closer together. Residues
which is involved solely in the Calcium-dependent regulation on the opposite end of the attached helices move away to
of skeletal and heart muscle contraction. Yeast (yCaM) is each helix with a greater difference in the orientation of
60% identical in sequence to vertebrate CaMs and contains Helix I (26 ) and IV (22 ) in the N-terminal than in that
only three functional sites. Several labs have shown that the of helices V and VIII in the C-terminal (for 15 and 10 )
prokaryotes have several CaM-like proteins containing two or suggesting that the N-terminal is more open than the C-
more authentic EF-hand motifs.21,82 terminal. This movement of helices results in the exposure
As the major calcium-signaling molecule, calmodulin of the hydrophobic residues required for the binding of the
relays initial calcium signals to a large number of functional target molecule (in the open conformation) and the helices
proteins in various physiological activities. This signal become more perpendicular.74,78,85 A harmonic oscillation
mediation is carried out by calmodulin-target protein of the central helix is observed across an arc with 20 .
interactions. Calmodulin binds to different target molecules Residues 77 81 are located in the middle of this central
at different calcium concentrations and results in different helix and act as a flexible tether, allowing conformational
effects.83 Some proteins, such as phosphorylase kinase, bind changes and cooperativity between the two domains in both
to CaM all the time but are only activated in the presence the calcium-bound form88 and the calcium-free form.78,85
of calcium. Similar to phosphorylase kinase, myosin light Significant backbone plasticity also was revealed by high-
chain kinase (MLCK), or calcineurin bind to CaM at both resolution 1.0 A X-ray structure of the calcium-loaded form
high and low calcium concentrations. This binding process of CaM from paramecium tetraurelia.89 Finally, Fallon and
is reversible possibly owing to its relatively weaker affinity Quiocho reported that the 1.7 A X-ray structure of a new
to CaM. The binding of CaM either inhibits the protein native calcium-CaM is in a compact ellipsoidal conformation
functions, such as in some of the G-protein-receptor kinases and shows a sharp bend in the linker helix and a more
and type-I IP3 receptors, or activates the protein function, contracted N-terminal domain.90
as in protein kinases I and II. In protein kinases I and IV,
the binding of CaM to two proteins (CaMK and CaMKK) 3.2.2 Calmodulin-dependent Proteins
simultaneously is required for the activation. Some proteins,
as neuromodulin and neurogranin, bind to calcium-free CaM Calmodulin-dependent Kinases. Calmodulin-dependent
instead of the calcium-loaded form.83,84 In the past few kinases further relay and amplify the calcium signal from
years, significant progress has been achieved in understanding calmodulin to their target proteins. In animals, the identified
calcium-dependent conformational changes and the several calmodulin-dependent kinases include CaM-dependent kinase
different interaction modes of calmodulin-target protein have kinase (CaMKK), CaM kinase I-IV (CaMKI-IV), in which
been reviewed. The calmodulin-target protein interaction CaMKII is also known as elongation factor-2 kinase (eEF-
is studied mostly by CaM-peptide complex. The peptides 2K), MLCKs and so on.84 CaMKK, CaMKI, CaMKII,
for CaM binding share no primary sequence homology. and CaMKIV have multiple targets that involve them in
However, some features are observed in many but not all multiple activities, while eEF-2K and MLCK have much
cases, such as the potential to fold into a basic, amphiphilic more restricted targets. CaMKK is at the upstream of the
-helix, and the large hydrophobic residues at positions CaMKI and CaMKIV kinase cascade. CaMKK activates
1 5 10 or 1 8 14.84 Here, we will first briefly discuss CaMKI and CaMKIV through the phosphorylation of these
calcium-dependent conformational changes of calmodulin. two kinases. The other substrate for CaMKK is protein kinase
We will then discuss some of the proteins involved in B (PKB). The activity of CaMKK itself is inhibited by protein
8 CALCIUM-BINDING PROTEINS
kinase A (PKA) that phosphorylates two sites in CaMKK.84 eEF-2K can be regulated by autophosphorylation and PKA.
Figure 7(a) shows a 26-residue peptide from CaMKK that Other kinases regulated by calmodulin include phosphorylase
binds to calmodulin (1IQ5).79 This peptide forms an -helix kinase, phosphatidylinositol 3-kinase, and a series of plant
at the N-terminus and a -hairpin at the C-terminus. The kinases such as cabin1, MCKs, CCaMKs, and CBKs, and so
peptide is engulfed between the two lobes of CaM and its forth.83,84,9395
C-terminus interacts with the C-terminal lobe of CaM. Two
major CaM-peptide contacts are located at Trp-444 in the Calmodulin-regulated Ion Channels. Calmodulin regu-
-helix and Phe-459 in the -hairpin of the peptide, which lates different ion channels including calcium channels. Here
has a 14-residue gap, longer than the normal 8- or 12-residue we briefly discuss the CaM-regulated potassium channel and
space. This binding mode is different from other peptides from sodium channel. All calcium channels and calcium pumps
CaMKII (Figure 7b) and MLCK (Figure 7c), which bind the will be discussed in Section 5 in this article. The voltage-
C-terminal lobe of CaM with the N-terminus of peptide. gated sodium channel has been shown to be regulated by the
CaMKI is located in cytoplasm and nuclei and is likely CaM-dependent pathway.96 The calcium-activated potassium
to participate in regulation of gene transcription. In vitro channel transports potassium from the cytoplasm to the extra-
CaMKI phosphorylates substrates such as synapsin and the cellular environment with a high selectivity for potassium
cystic fibrosis transmembrane regulator although its in vivo over sodium. Its function is dependent on the cytoplasmic
substrates are yet to be identified. CaMKI is activated by calcium concentration instead of the membrane potential.
phosphorylation by CaMKK when both kinases are calcium Calcium increases the frequency of channel opening rather
and CaM bound. The 25-residue CaM-binding peptide of than the duration time of each opening. The potassium chan-
CaMKI forms an -helical structure. Two hydrophobic nel functions as a homo-tetramer. Each monomer contains
residues are located at positions 1 and 14 (Trp-303 and six transmembrane segments (TMS) and a pore between
Met-316). The peptide induces the bending of the central helix TMS-5 and TMS-6. Both the N- and C-termini are located
with the interaction of both the N- and C-domains of CaM on the cytosolic side. CaM binds to the C-terminus of the
(pdb 1MXE).84,91 protein.95,97
The CaMKII family phosphorylates numerous substrates Figure 8 shows the structure of the CaM complex with a
including NR1, NR2A, NR2B, F-actin, -actinin, densin- 96-residue fragment of the C-terminal cytosolic region of the
180, synGAPb, and cdk5.92 CaMKII is not a substrate of other channel with a different protein protein interaction compared
kinases. However, with the binding of calcium/CaM, it rapidly to the CaM-peptide structures.98 This complex forms a dimer
undergoes autophosphorylation at Thr-286 to activate itself. over two extended CaM molecules. The potassium channel
Once phosphorylated, the kinase activity is partially retained
even after the calcium/CaM dissociates from the protein.
Figure 7(b) shows that the binding of CaMKII peptide to CaM
unwinds the central helix of CaM (Figure 6). The C- and
N-lobes of CaM are bent by 100 and rotate by 120 relative
to the substrate-free calcium-bound CaM. Thus, the N- and
C-lobes of CaM close together to form a hydrophobic pore
that holds the peptide. The binding is mainly driven by the
hydrophobic forces where the methionine residues in CaM
play a critical role. MLCK has as substrate the regulatory light
chain of myosin II. A 25-residue peptide interacts with CaM (a)
in a manner similar to that of the other kinase peptides. It
bends the central helix of CaM to enable interaction with both
lobes of CaM. The peptide forms -helical structure and the
Trp-4 and Phe-17 (positions 1 and 14) of the peptide anchor
the peptide to the C- and N-terminus of CaM, respectively
(Figure 7c).80,84
CaMKIV is responsible for calcium-dependent gene
transcription through the phosphorylation of transcription
factors cAMP response element-binding protein (CREB),
serum response factor (SRF), and myocyte enhancer factor-2 (b)
(MEF2). Oncoprotein 18 in the cytoplasm is also a substrate
of CaMKIV. The activity of CaMKIV is activated by CaMKK
Figure 8 The structures of CaM complex with the peptides from
and autophosphorylation. The elongation factor-2 is the (a) a 96-residue fragment of the C-terminal cytosolic region of the
only known substrate of CaMKIII (eEF-2K) at present. The potassium channel (1G4Y) (yellow and pink)98 and (b) calcium pump
phosphorylation of elongation factor-2 inhibits its functions. (yellow, 1CFF)99
CALCIUM-BINDING PROTEINS 9
fragment forms two antiparallel -helices with the shorter one catalytic site alone has no obvious difference between the
binding to the C-terminal lobe of CaM only. On the other hand, CaM-free and loaded forms. Nevertheless, CaM binding
the N-terminus of the longer -helix binds to the C-terminal enhances the activity of edema factor 1000-fold.100 Further,
lobe of CaM and the C-terminus of this helix protrudes to an -helical peptide of exotoxin contains a typical CaM-
bind to the N-terminal lobe of another CaM. In this structure, binding hydrophobic pattern at positions 1-5-10. The NMR
CaM is half saturated. Two calcium ions are bound at the and Fluorescent resonance energy transfer (FRET) studies
N-terminus of CaM. Surprisingly, the C-terminal lobe with a demonstrated that upon binding to this peptide, CaM is bent
higher calcium affinity is free.95,98 with both the N- and C-lobes moving close together in a
manner similar to that of CaM-dependent kinases (Figure 7).
It is possible that CaM binds to the short peptide and the
Nucleotide Cyclases. Calmodulin regulates the activity
full-length protein in different topologies.95,100
of different nucleotide cyclases such as adenylyl cyclase
that catalyzes the formation of cAMP from ATP. cAMP is
another important molecule in the cell functioning as a second- Other Enzymes and Proteins. In addition to the kinases,
messenger like calcium. The calmodulin-adenylyl cyclase cyclases, and ion channels, CaM interacts with and regulates
interaction links these two second messengers together.83,95 a large, growing number of target proteins from almost
Edema factor of anthrax is one of the three exotoxins every physiologic event of life. These target proteins include
produced by the bacteria. The primary sequence is only enzymes such as phosphodiesterases or phosphatase and other
slightly homologous to other adenylyl cyclases. When it proteins such as gap junction protein connexins or -2-
enters the host cells, edema factor acts as an adenylyl cyclase glycoprotein.83,95 Recently, the structures of CaM-peptide
and transforms ATP to cAMP efficiently. The structure of complexes from two enzymes have been solved, one is
CaM-edema factor of anthrax complex has been obtained glutamate decarboxylase and the other is Nitric oxide
(Figure 9).100 In the CaM-edema factor complex, only the synthase (NOS). NOS catalyzes the synthesis of NO, an
C-terminal lobe binds two calcium ions while the N-terminal important physiological messenger and cytotoxin. The 20-
lobe is empty. CaM remains extended and is deeply inserted residue peptide from NOS binds to CaM to form a structure
between the catalytic and the -helical domains of this similar to that of CaMK peptide. The NOS peptide is -helical
exotoxin with a large number of residues of CaM involved and contains a classical pattern with hydrophobic residues at
in the interaction. CaM binding results in a large domain positions 1 5 8 14. Phe-496, Ala-500, Val-503, and Leu-
reorientation of edema factor. The helical domain of edema 509 in this pattern form critical interactions with CaM. In
factor undergoes a 15 A translation and a 30 rotation. The addition, Ile-505 interacts with several CaM residues such as
CaM inserted site is far from the catalytic site and the Met-76, Phe-12, and Ala-15. The central helix of CaM is bent
to wrap the peptide inside the pore.101
Glutamate decarboxylase in plants is a necessary enzyme
for plant growth. It regulates glutamate metabolism and con-
verts the glutamate into CO2 and -aminobutyrate (GABA).
The 26-residue peptide from glutamate decarboxylase is pre-
dominately unstructured in the absence of CaM. It becomes
-helical upon binding CaM (Figure 7d). Instead of a 1:1 bind-
ing, glutamate decarboxyase peptide binds to CaM in a 2:1
ratio. The N-terminal and C-terminal domains of CaM each
bind one peptide. The two peptides are antiparallel forming an
(a) X-shape with an angle of about 60 . Trp-485 and Ile-482 are
the two anchor residues and are critical for peptide-CaM inter-
action. CaM also bends and the two lobes move close together
in this structure with a domain orientation different from that
of CaMK peptide-CaM complex. For example, the interhelical
angle between CaM helices 4 and 5 is from 114.2 to 123.2
in CaMK peptide complex while in glutamate decarboxylase
peptide complex it is 17.2 .81
3.3 Troponin C
(b)
Tropinin C is a trigger protein that responds to the
intracellular calcium concentration in striated muscle cells.
Figure 9 The structures of (a) calmodulin-free (1K8T) and An increase in calcium concentration up to 105 M results in
(b) calmodulin-bound (1K93) forms of Edema factor100 calcium binding to TnC. The binding of calcium to TnC allows
10 CALCIUM-BINDING PROTEINS
(a) (b)
Figure 10 (a) The structures of sTnC with two calcium ions bound.103 (b) The NMR structures of four-calcium-bound cTnC with the
C-terminal of the protein superimposed104
it be recognized by the thin filament proteins to regulate muscle of cTnC remain in a predominantly closed conformation upon
contraction. The thin filaments contain tropomysin, actin, and calcium binding.102
troponin. Troponin is a complex of TnC, troponin I (TnI),
and TnT. The thick filaments are composed of myosin and
a large ATP binding multi-subunit. Calcium binding to the 3.4 Calcium-buffer Proteins: Parvalbumin and
low affinity of the N-terminal domain of TnC results in a CalbindinD9K
conformational change, which, in turn, causes an alteration in
the TnC/TnI/TnT interaction. The signal is then transmitted to Different from trigger proteins, parvalbumin and
other members of the thin filament. The interaction between calbindinD9k function as calcium-buffer proteins. Calcium
the thin and the thick filaments are modified and muscle binding to both proteins does not lead to conformational
contraction is initiated.102 change with an exposed hydrophobic surface. The struc-
TnC has two isoforms of sTnC in fast striate muscle and ture of a carp parvalbumin was the first structure in the
cTnC in slow skeletal-cardiac muscle. Both isoforms contain EF-hand protein family.59 It has two isoforms ( and )
four EF-hand calcium-binding sites. Site I of cTnC is inactive with very similar structures. Oncomodulin is the mammalian
for calcium binding. Like calmodulin, EF-hand motifs I and II beta linkage parvalbumin. The structure of parvalbumin com-
are paired in the N-terminal domain and III and IV are paired prises three helix-loop-helix motifs, called AB, CD, and EF
in the C-terminal domain. The 3D structures of sTnC from initially (Figure 11). The calcium-binding loop in the first
both chicken and turkey were first solved in 1985 and refined
in 1988. As shown in Figure 10, the calcium-binding sites in
the C-terminal domain are occupied while two calcium sites
in the N-terminal domain are empty. The apo-N-terminal has
different interhelical angles. Based on these observations and
molecular modeling, Herzberg et al. proposed the HMJ model
for the conformational change that occurs in the N-domain
of TnC upon calcium binding. In the model, calcium binding
leads TnC to change from a closed form to an open structure.
The B/C pair of the helices is moved away from the A/D
pair, which, in turn, exposes a hydrophobic patch. Since then,
many structures of TnC with zero, two and four calcium ions (a) (b)
bound have been solved. There are several surprises. First, the
NMR structures of the calcium-loaded form of sTnC have a
Figure 11 Structures of (a) parvalbumin and (b) CBD. Parvalbumin
large flexibility in the interdomain linker. Hence the relative contains three EF-hand motifs, two of them bind to calcium (purple)
orientation of both domains is not fixed (Figure 10b). Second, and one loses the calcium-binding ability (orange).105 CBD is
both the N-terminal domain in isolation and the intact protein monomer while the other S100 proteins are dimer106
CALCIUM-BINDING PROTEINS 11
calcium-binding site has a deletion of two residues. Hence to the phosphorylation positions. For example, S100
this protein binds two calcium ions in the tightly coupled members regulate the annexin-membrane association by
CD and EF calcium-binding sites. Although the AB site does preventing annexin phosphorylation. The inhibition of p53
not bind calcium, it is not nonfunctional since it stabilizes protein phosphorylation by S100A4 and S100B affects cell
the calcium-loaded form by covering its hydrophobic surfaces growth and tumor occurrence. The phosphorylations of
and the calcium-binding affinity is dramatically reduced once myristoylated alanine-rich C kinase substrate (MARCKS),
the AB site is deleted. The role of parvalbumin is proposed myosins, caldesmons, and protein are also regulated by their
to relax muscle after calcium-simulated contraction. Recently S100 partners. Third, S100 proteins control cell morphology,
parvalbumin has also been shown to play a role in neuron cells. motility, and the dynamics of certain cytoskeleton elements.
CBD is the smallest EF-hand protein with two EF-hand The components of the cytoskeleton system are a target for
motifs. As a member of the S100 protein family, CBD contains many S100 members. For example, microtubules interact
one canonical and one pseudo-EF-hand motif at the C-terminus with S100A1/S100B. Type-III intermediate filaments (IFs)
and N-terminus of the protein, respectively (Figure 11). interact with both the S100A1/S100B and S100A8/S100A9
Unlike other S100 proteins, CBD remains monomeric in complex. Caldesmon interacts with S100B and S100A6.
solution. Chazin and Forsens groups have carried out Myosin interacts with S100A4. Tropomyosin interacts with
extensive structural studies of CBD at different conditions. S100A4 and S100A2. Microfilaments interact with S100A4
Like parvalbumin, no significant structure changes have been
and S100A1. CapZa interacts with S100A1. F-actin interacts
observed upon calcium binding.77,107
with S100A11. Keratin IFs interact with the S100A8/S100A9
complex and three other S100 members, profilaggrin,
3.5 S100 Proteins trychohyalin, and repetin.67,109,111 Fourth, S100A1 has also
been suggested to have chaperone activity as Hsp70/Hsp90.112
The S100 (initially named after soluble in 100% ammonium Fifth, monomeric CBD buffers cellular calcium concentrations
sulfate) proteins are a group of low molecular weight, soluble (Section 3.4).67,109
calcium-binding proteins.108 Currently there are more than 20 Many S100 proteins function extracellularly although the
members in this family. Members of the S100 family often secretion mechanism is not quite clear. S100B stimulates
have more than one name. Genes encoding S100A1 14 are neurite extension at nM concentration but inhibits it at M
clustered together at the human chromosome region 1q21. concentration. S100B also induces neuronal apoptosis, IL-6
All S100 members form dimers or oligomers except CBD. secretion, and NO secretion, modulates synaptic plasticity,
The tendency of dimerization is very strong with a Kd in and inhibits myogenesis. The S100A8/S100A9 complex
the nanomolar range. This dimerization or oligomerization plays a role in the immune system. It has cytostatic and
is critical for S100 proteins to interact with target proteins. antimicrobial activities. At the same time, it inhibits the
It is interesting to note that CBD is the only monomeric activity of macrophage and the synthesis of immunoglobulin.
S100 member that does not mediate any protein protein S100A8/S100A9 complex also stimulates CD11b expression
interactions; instead it functions as a calcium-buffer protein.
and inflammation response. S100A12 stimulates neurite
Most of the S100 members are observed in homodimers
growth at M concentration and causes monocyte migration
while S100A8 and S100A9 prefer to interact specifically with
at nM concentration. The other extracellular S100 functions
each other to form a heterodimer. The S100 family was
include S100A10 inhibiting the extrinsic pathway of blood
first identified as intracellular functional proteins expressed in
coagulation, S100A2 inhibiting tumor cell motility, S100A4
specific cells; for example, S100A8/A9 are mainly expressed
stimulating neurite extension, and S100A2 and S100A4
in myeloid cells. Some S100 proteins have been shown to
function extracellularly.67,108111 mediating chemotactic processes.67,109,113
The intracellular functions of S100 proteins can be S100 proteins contain two calcium-binding sites, one
summarized as follows: First, the interactions between S100 canonic EF-hand site at the C-terminus (helix III-loop-helix
proteins and their target proteins result in either stimulating or IV) and one pseudo-EF-hand site at the N-terminus (helix
inhibiting enzyme activities. The enzyme stimulation effects I-loop-helix II) (Figure 5). Calcium binds to these two sites
have been observed in cases of S100A1 and S100B binding cooperatively.62,109,111 The majority of the S100 functions
to fructose-1,6-bisphosphate aldolase, phosphoglucomutase, are calcium-dependent, but calcium-independent S100-target
twitchin kinase, and membrane-bound guanylate cyclase protein interactions have also been observed.111 The apo-,
and S100B binding to Ndr. The enzyme inhibition effects holo-, and target-binding-S100 triggers have been studied by
have been observed in the process of S100A11 binding NMR and X-ray crystallography. Figures 12 and 13 illustrate
to actomyosin ATPase, S100A10 binding to phospholipase the calcium-induced conformational change of S100A6 and
A2, S100A8/S100A9 complex binding to casein kinase I S100B.114117 The interaction surface of the dimeric structure
and II, and S100A1 binding to phosphoglucomutase and has small changes. The relative orientations of helices I, IV,
glycogen phosphorylase. Second, S100 binding inhibits I, and IV are almost the same before and after calcium
protein phosphorylation by blocking the access of kinases binding.67,111
12 CALCIUM-BINDING PROTEINS
IV I
IV
I III
II
III
III
II
II II
IV
III
I
I
(a) (b)
IV
IV
I III
II
II
III
IV
(c)
Figure 13 The structures of the calcium-free (a, 1SYM)115 and the calcium-bound (b, 1QLK)116 of S100B dimer (c). The structure of S100
dimer complexed to the target peptide (cyan in bottom figure, 1MWN)117 at the cleft of helices III, IV, I, and the helices II-III hinge
between domain II and domain III. However, the X-ray conditions, three calcium ions (green ball) bind to EF-1, EF-2,
structure of m-calpain indicates this EF-hand motif is not and EF-3. The other calcium (orange ball) located in EF-4
formed and does not bind to calcium. Instead, other loops is not chelated by the typical EF-hand residues. Instead, it
coordinate two calcium ions. Both domain VI (light chain) uses bidentate Asp-225 and Asp-223 together with Asn-226
and IV (heavy chain) contain five EF-hand helix-loop-helix and Asp-135. Additional studies suggest that calcium may
motifs with mutations. For example, EF-1 (termed from bind to different loops dependent on protein species and
N- to C-terminal) in both domains IV and VI has only 11 conditions. For example, a mutagenesis study has suggested
residues. The first two side chain ligands in typical EF-hand that the EF-2 and EF-5 of domain VI bind calcium ions.
are missing and a mainchain carbonyl from Ala is used as A truncated calpain domain VI structure (removal of EF-
a ligand. EF-5 is two residues longer than the normal EF- 5, 1NP8) shows all four remaining EF-hand motifs are
loop. The EF-5 of domain VI lacks the bidentate Glu at the occupied by cadmium ions. The removal of the EF-5 of
C-terminal. calpain domain VI abolishes the hetero-dimerization ability
As shown in Figure 14, domain VI of calpain (1ALV) has with the intact calpain domain IV suggesting that EF-5 is
eight -helices forming five helix-loop-helix motifs.121 Of the responsible for the dimerization. On the other hand, the
eight helices, helix-4 is shared by EF-2 and EF-3 and helix-7 truncated protein forms homodimer through different contact
is shared by EF-4 and EF-5. Under the crystal experimental surfaces.120,122
14 CALCIUM-BINDING PROTEINS
3.7.1 Calcineurin
recoverin (e.g. 1REC, 1OMR, 1IKU, and 1JSA), neurocalcin Below we will present how different extracellular calcium
(1BJF), and frequenin (1FPW and 1G8I).133137 proteins carry out their unique biological functions.
DREAM dimerizes and tetramerizes through a calcium-
dependent mechanism. The calcium-free DREAM forms
tetramer at protein concentrations higher than 20 M. The 4.1 Cadherins
calcium-bound DREAM forms dimer at low protein concen-
trations and tetramer when protein concentration is higher than Cadherin family refers to a group of calcium-dependent
200 M. There are other recoverin-like proteins with calcium- homophilic cell cell adhesive molecules (Figures 17 18).
dependent dimerization with different responses. For example, Typical cadherins are named based on their expression
calcium-free neurocalcin is a monomer while the calcium- locations, such as E-cadherin (epithelial), M-cadherin
loaded one forms a dimer. Conversely, guanylyl cyclase acti- (muscle), and N-cadherin (neuron). Atypical cadherins include
vating protein 2 (GCAP-2) forms a dimer in the calcium-free T-cadherin (truncated) and protocadherins.11,139,140 Cadherins
state and becomes a monomer in the calcium-bound state.93 are the major constituent of the cell cell adhesive junctions,
To repress transcription, the calcium-free DREAM tetramer functioning together with numerous other proteins such as
binds to DNA. Upon calcium binding, DREAM becomes a catenins.11,139141 The property of homophilic recognition of
dimer and leaves the DNA to allow the RNA polymerase to cadherins and the formation of adhesive junctions play a key
perform transcription.93 URE3-BP is another EF-hand protein role in morphogenesis. For example, selective expression
that directly interacts with DNA at the upstream regulatory of different cadherins controls selective cell aggregation,
element-3 of the lectin heavy subunit gene. This protein has which refers to the suspended cell re-aggregation with
two EF-hand motifs.138 only homotypic cells.140 This process is important in tissue
and organ development. Cell condensing, another process
in morphogenesis, also requires cadherins. Central nervous
system development represents one of the most striking
examples of cadherin-regulated morphogenesis. More than
4 EXTRACELLULAR CALCIUM-BINDING
20 different cadherins, involving all key events of neuron
PROTEINS
formation from the beginning stage of cell aggregation to
the formation of synapses, are expressed at different stages
There are several types of extracellular calcium-binding and structural layers. Neurite outgrowth is also activated
proteins. The majority of these proteins such as cadherins, and regulated by cadherin expression. The formation and
integrins and growth factors, are from eukaryotic systems. regulation of junctions between two neurons or neuron-muscle
E11
E69
O101
D100
N102
D67
D136 D103
N143
N104
D195
D134
(a) (b)
Figure 17 The dimeric structure of E-cadherin EC1 2 (1EDH) (a).142 Two polypeptide chains and their bound calcium are shown in different
colors. (b) A close-up view of the calcium-binding sites. The calcium ligand residues on chain A are labeled. Several ligands are shared by
different calcium ions. All calcium binding in cadherin belongs to the discontinuous site class
CALCIUM-BINDING PROTEINS 17
are also cadherin-dependent. The role of cadherins, especially domains are also different from those of classical cadherin.
that of E-cadherins, in cancer growth and tumor invasion, Furthermore, they have different intracellular tails that do not
has been investigated. Abnormal expression or abnormal interact with catenin.140,144
distribution of E-cadherins has been observed in several The intracellular tail of classic cadherin interacts with -
cancers.140 catenin or -catenin directly.139,140 -Catenin interacts with
Classical cadherins comprise three different parts, an the cadherin tail through the mediation of -catenin. Catenins
intracellular C-terminal tail, a transmembrane segment then interact with the cytoskeleton protein actin. Through
that spans through the cell membrane once, and a long this cadherin-catenin-actin complex, cell cell adhesion is
extracellular N-terminal chain.139,140 The extracellular chain linked with the cytosolic signal pathway. The cadherin-
contains five domains termed EC1 5 (Figure 18). Each catenin complex regulates the outside cell cell interaction.
domain is 110 residues. The extracellular five domains The expression level of cadherin also affects the expression
are highly homologous to each other. The first domain of catenins. Another group of cadherin tail binding molecules
at the N-terminus (EC1) is directly involved in cell cell is the p120 subfamily, which has a structure similar to
interaction. Domain exchange experiments have shown that catenins.139 Extracellular cell adhesion is regulated by
the homophilic adhesive properties are encoded in the EC1 modifying the intracellular cadherin tail and its target.
domain. Substitution of E-cadherin EC1 domain with P- Stimulated by different signals, such as epidermal growth
cadherin (placental) EC1 domain leads the protein to bind factor (EGF), transforming growth factor , platelet-derived
selectively with P-cadherin. The four repeated domains growth factor, hepatocyte growth factor, hormones, signals
EC2 5 are required for the maintenance of normal cadherin from gap junctions, and cholinergic receptor agonists, catenins
function. On the other hand, atypical cadherins of T-cadherin or p120 will be phosphorylated directly or indirectly.
(truncated) and protocadherin subfamily have different Phosphorylation and dephosphorylation states of catenins or
structural properties.140,144 T-cadherin (truncated) expressed p120 alter the cadherin-target complex and further control the
in the neuronal system does not have the transmembrane extracellular function of cadherin. This process is controlled
and intracellular parts. It is anchored on the cell membrane by PKC, several signal receptor tyrosine kinases, Src tyrosine
via glycosylphosphatidylinositol (GPI). The extracellular part kinase, and several protein tyrosine phosphatases.139,141
still contains five domains but without the conserved HAV The 15 solved structures of cadherins are mainly E- and
sequence in EC1. The protocadherin subfamily has six or N-cadherin. The X-ray structure shows seven -strands in the
more extracellular domains. The sequences of EC3 and EC5 EC1 domain. As shown in Figure 17, the EC1 2 domains
of E-cadherin form lateral dimers in a calcium-dependent
manner. There are three calcium ions bound between EC1-EC2
domains in each monomer in the crystal structure of E-cadherin
EC1 2 dimer (1EDH).142 Some ligands are shared by different
calcium ions (Figure 17). The residue ligands for Ca1 are from
the side chain of Glu-11, Asp-68, Glu-70, and Asp-103. The
side chain carboxyl oxygen atoms of Glu-11, Glu-70, and
Asp-103 are used as the ligands for Ca2. Ca2 also shares
ligand Asp-136 with Ca3. The additional residue ligands for
Ca2 are the side chain of Asp-100 and the mainchain of
Gln-101. In addition to Asp-136, the ligands of Ca3 include
bidentate Asp-134, the side chain of Asn-102, Asp-195, and
the mainchain of Asn-104 and Asn-143.142 Boggon et al.
recently reported the structure of full-length ectodomain of
the C-cadherin (EC1 5) (Figure 18).143 Twelve calcium ions
bind to the linkage region between neighboring domains, three
in each of the four regions to sequentially organize the protein.
The HAV tripeptide sequence in EC1 domain has been shown
to be important for homophilic recognition.143 The binding
of calcium induces the conformational change of cadherin,
including the important process of the Trp-2 in EC1 docking
into the HAV sequence, which is believed to be important in
exposing the homophilic recognition region. Trp-2 is observed
Figure 18 The structure of the extracellular region of Ep-cadherin both in cis dimerization and trans orientation (Figure 17). The
(1L3W).143 Calcium ions bind to the loops between each two adjacent
domains and the whole protein in the structure forms a curvature. structure of the five domains has a gentle bend without applied
N-acetyl-D-glucosamine molecules attached to the cadherin surface forces. This orientation corresponds to the distance of adhesion
are in gray junctions revealed by EM. Cadherin monomers on opposed
18 CALCIUM-BINDING PROTEINS
4.2 Integrins
Before 2000, only structural information of the A- 4.3 Calcium-dependent Epidermal Growth Factor
domain was available. Several X-ray and NMR structures (EGF)
of the extracellular integrins have been obtained after 2001
and they revealed detailed metal ion and peptide binding A large protein family that contains extracellular domains
information.145,150,151 These structures include the v3 homologous to EGF is called the EGF-domain proteins. EGF-
with (1L5G)150 and without (1M1X and 1JV2)150,151 RGD like domains or modules are often found in many extracellular
sequence, the NMR structures of the N-terminal domain of and membrane proteins (>70). They are involved in blood
Iib3 (1KUP and 1KUZ),152 and the NMR structure of 2 coagulation, fibrinolysis and the complement systems, matrix
subunit EGF-like domain (1L3Y).153 The overall structure of proteins, cell surface receptors, the low-density lipoprotein
the extracellular segments of integrin is like a head with two receptor and the developmentally important receptor, Notch.
legs. The head consists of a -propeller domain, including EGF-like domains may exist as multiple copies within proteins
A domain also in some types, of the -subunit and the A such as in the Drosophila protein Notch with 36 copies or as a
single copy as in EGF itself. It can also be found in conjunction
hybrid domains of the -subunit. These two legs can be bent
with other modules.
or extended depended upon different ligand and metal ion
EGF-like domains usually contain 40 50 amino acids
binding. The transition positions of these two conformations
with 6 conserved cysteine residues that form three disulfide
(bent and extended) are located between the thigh and calf-1
bonds pairing in the pattern of 1 3, 2 4 and 5 6. These three
domain in the -subunit and PSI, EGF1, and EGF2 region in
disulfide bonds stabilize their common structure of two regions
the -subunit. The crystal structure 1M1X (3.3 A, Mn-loaded)
of double-stranded antiparallel beta sheets (Figure 21). More
and 1JV2 (3.1 A, Ca-loaded) revealed six divalent ion-binding
than 25% of EGF modules bind calcium. They are called
positions.150,151 As shown in Figure 20, four calcium-binding
calcium-binding EGF (cbEGF) and form one of the most
sites are found at the repeated blades 4 7 of the -propeller
popular extracellular calcium-binding sites. cbEGF is usually
structure at the N-terminal of -subunit. They are exposed to
phlogenetically related and clusters together in a dendrogram.
the solvent with a continuous calcium-binding loop similar to
Fibulins, a newly recognized family of extracellular matrix
the EF-loop of glactose-binding proteins, where a conserved
proteins, have tandem arrays of EGF-like domains.154
nine-residue segment of D-h-D/N-x-D/N-G-h-x-D contains
The coagulation and anticoagulation proteases, factors VII,
all the calcium-binding ligands at the side chain of positions
IX, and X, and protein C, have a common domain structure
1, 3, 5, and 9 and the mainchain of position 7. The h here
with an N-terminal gamma-carboxyglutamic acid (Gla)-
refers to hydrophobic residue and x refers to any residue.
containing domain that is followed by two EGF-like modules,
Another calcium ion binds to -subunit between the bottom whereas the C-terminal half of each protein is occupied by
of the thigh domain and the top of the calf-1 domain. a trypsin-like serine protease domain. Prothrombin also has
A-domain holds calcium at the ADMIDAS (adjacent to an N-terminal Gla domain and a C-terminal serine protease
metal-ion-dependent adhesion site (MIDAS)) region, which
coordinates the calcium by the mainchain carbonyl of Ser-123
and Met-335 and the side chain carboxyl of Asp-126 and Asp-
127. When the protein is exposed to the manganese buffer, all
six calcium-binding sites can be occupied by manganese.150,151
A MIDAS has been proposed in the A-domain in the
A-containing integrin, as also in the A-domain, which is
the recognition location for the ligand molecules. The MIDAS
motif of A binds magnesium or manganese with high affinity
and binds calcium with low affinity.145,150,151 The RGD peptide
binds to the A and -propeller structure of v3 resulting
in the disruption of a hydrogen bond between Asp-119 and
Glu-220 to allow the Glu-220 function as a ligand for the
additional metal binding at the MIDAS motif.150,151 This
metal ion is coordinated with the carboxyl of Asp-119, Asp-
251, and Glu-220, and the hydroxyl of Ser-121 and Ser-123.
The binding of the short peptide RGD resulted in the binding
of a second metal ion. This second metal ion is also located
around the MIDAS motif with the ligand oxygen atoms from
the side chain of Glu-220, Asp-158, Asn-215, and Asp-217,
and the mainchain of Asp-217 and Pro-219. Glu-220 provides
its two side chain carboxyl oxygen atoms to both metal ions. Figure 21 The structure of two EGF-like domains in human
Although these two sites are revealed in the manganese bound low-density lipoprotein receptor is shown with the Cys (violet)
structure, all the ligands are popular in calcium binding.150,151 highlighted155
20 CALCIUM-BINDING PROTEINS
domain, but they are separated by two so-called kringle P-, I-, R-, C-type lectins, and galectins, in which C-type lectins
domains rather than EGF-like domains. are calcium-dependent lectins. C-type lectins are composed of
A protein S, the cofactor of activated protein C, has four several different subfamilies, including collectins, selectins,
EGF-like modules in tandem. The structure of N-terminal the mannose receptor, and NK receptors and so on. They
EGF modules is very similar to that of non-calcium-binding are normally multiple domain proteins that comprise calcium-
modules. Calcium binding only results in a limited local dependent CRD domain(s) and other domains performing
conformational change. The N-terminal loop is better defined diverse functions. The CRD domain in C-type lectins adopts
and moves toward the major -sheet. The N-terminal non- a mixed / structure.166,167 This section will briefly discuss
catalytic Gla and EGF-like domains provide coagulation the major C-type lectins of collectins, mannose receptor,
serine proteases with different calcium affinities for certain selectins (CD62), asialoglycoprotein receptor (ASGPR) and
biological membranes, and also mediate protein protein GBPs. Calnexin and calreticulin will be discussed in the
interactions.156,157 ER/SR calcium-binding protein section.
Fibrillin-1 is composed of 43 cbEGF-like domains.158
Calcium binding of fibrillins stabilizes interdomain cbEGF
interactions and has been shown to be responsible for the 4.4.1 Collectins
formation of a rod-like linear arrangement. In addition, cal-
cium binding significantly protects full length or recombinant Collectins are the soluble extracellular members of the
fragments of fibrillin-1 from proteolysis by trypsin, elastase, lectin family. Collectins are secreted to the extracellular
endoproteinase Glu-C, plasmin and matrix metalloproteinase. matrix and function as sugar pattern recognition molecules
cbEGF contains more than 60% of the identified mutations that selectively interact with certain microbial surfaces. It
of the connective tissue disease Marfan syndrome and related is important for immune responses. Mannose binding lectin
disorders. Mutations at calcium-binding consensus residues (MBL) (mannose binding protein (MBP)), surfactant protein
on cbEGF such as N2144S in cbEGF32 significantly reduce A (SP-A), SP-D, conglutinin, collectin-43, and collectin liver-
calcium affinity. Recently NMR studies of the solution struc- 1 belong to the collectin subfamily.167169 The collectins
ture and dynamic properties of the cbEGF pairs such as comprise four segments: a Cys-containing N-terminal segment
cbEGF12 13 reveal a correlation between calcium-binding that provides inter- and intrachain disulfide bridges, a collagen-
affinity and backbone dynamics. Calcium plays a key role like (-Gly-X-Y)n repeating sequence, a short linkage between
in stabilizing the rigidity of the domain pair on the pico-to- the collagen-like segment to the CRD domain, and the calcium-
millisecond timescale.159,160 dependent CRD domain at the C-terminal.169 As shown in
The calcium-binding site in EGF domain is characterized Figure 22, the collectins form trimers in which collagen-like
by a consensus D/N-x-D/N-E/Q-xm -D/N-*-xn -Y/F (where m segments wind together and their CRD domains are clustered
and n are variable and represents beta-hydroxyaspartic acid at the top of the collagen helices. The isolated CRD with
(Hya) or erythro-beta-hydroxyasparagine (Hyn). Hydroxyla- linkage segment maintains trimeric structure and the CRD
tion is carried out by Asp/Asn-beta-hydroxylase. Factors IX without the linkage segment forms a dimer. Both sugar-
and X and protein C all have one Hya in the N-terminal EGF selective and calcium-binding properties are encoded in the
module. There are two types of calcium-binding sites. Calcium CRD domain; for example, Glu-185 and Asn-187 in MBP-
sites largely locate between domains involved in conserved A are specific for mannose recognition, but when they are
acidic residues in one EGF-like module and a single calcium mutated to Gln-185 and Asp-187, the protein changes its
ligand from a neighboring repeat. In Class I of repeat pairs, preference to galactoside.169
one ligand is donated by the N-terminal adjacent EGF-like Calcium binding is required not only for function but
domain161 while for Class II, this ligand is from a repeat on an also for structure stabilization. Here we use rat MBL A
adjacent molecule.10 Calcium-binding sites are usually pen- (1RTM)170 as an example to illustrate the calcium binding in
tagonal bipyrimidal. Usually isolated domain modules have collectins (Figure 22). Each monomer contains three calcium
low calcium affinity (1 6 mM). The calcium affinity of the ions. Each CRD binds two calcium ions specifically (Ca1
module pair was shown to be increased by 10 20-fold (Kd is and Ca2) and one nonspecifically. As shown in Figure 22(b),
about 0.1 mM).162 N-terminal neighbor usually influences the Ca1 is coordinated by the sidechains of Asp-161 (bidentate),
calcium affinity of cbEGF modules.163 Asp-188, Asp-194, Glu-165, and the mainchain carbonyl of
Glu-193. Glu-193 provides the ligands for both specifically
bound calcium ions. Ca2 is coordinated by the protein ligands
4.4 C-type Lectins of sidechains of Glu-193, Glu-185, Asn-187, Asn-205, Asp-
206, and also the mainchain carbonyl of Asp-206. The bound
Lectins refer to all of the proteins that have carbohydrate- sugar provides two hydroxyl oxygen atoms as additional
binding abilities.164,165 Carbohydrate recognition domain ligands for Ca2. Meanwhile, this bound sugar interacts with
(CRD) is the functional part in lectins for sugar binding. Based Glu-185/Asn-187 pair, Asn-205, and Glu-193 of the protein.
on the structural diversity of CRD, lectins are classified as L-, Thus, Ca2 directly mediates the sugar binding.169,170
CALCIUM-BINDING PROTEINS 21
Sugar
E185
N205
Ca2
E193 N187
D206
D194
Ca1 D188
E165
D161
(a)
(b)
Figure 22 (a) The trimeric structure of MBL-A (1RTM)170 with each monomer labeled with a different color. The CRDs and the glycan-like
domains are labeled in dark and light colors, respectively. Each monomer contains three calcium ions. Two calcium ions (Ca1 and Ca2) that
are specifically bound to the CRD are in green. The nonspecific calcium is in the lighter color. The calcium-mediated bound sugars are labeled
in red. (b) The local view of the calcium-binding sites of Ca1 and Ca2 of MBL-A with ligand residues highlighted. Several ligands for both
calcium ions are highly clustered in the loop from residue 185194, while Glu-193 is shared by two calcium ions. Glycerol is shown in violet
The X-ray structure shows that human SP-D (1PW9),171 in many of the collectin members. Either acidic residue Asp
another collectin member, shares the same calcium-binding or Glu is used as a bidentate ligand for Ca1.
pattern as rat MBL-A, in which Ca2 binding ligands
are encoded in a 22-residue loop E-x-N-5x-E-11x-N-D
(Figure 23). The last Asp residue provides both mainchain 4.4.2 Mannose Receptor
and side chain ligands. Ca1 binding ligands are encoded in a
longer loop D-3x-E-22x-D-4x-E-D, in which the first Asp is The mannose receptor subfamily is a group of membrane-
bidentate and the second Glu is shared with Ca2. Sequence attached C-type lectins with multiple CRDs. Since most of
alignment reveals that similar sequence characteristic proper- these domains maintain neither calcium-binding nor sugar-
ties for calcium binding are also conserved in other collectin binding properties, the term C-type lectin-like domain (CTLD)
members. For example, the Ca1 and Ca2 sharing Glu-residue, is more frequently used lately instead of the term CRD.
the N-D pattern at the end of the Ca2 binding loop, and the The mannose receptor subfamily comprises four members
Glu-residue at the start of the Ca2 binding loop are conserved including the mannose receptor, the M-type phospholipase A2
80 82 88 105 106
Selectin (human E-selection)
Figure 23 Summary of the amino acid sequence patterns that are involved in calcium binding of the subfamilies of C-type lectins. One
example in each subfamily is shown and the ligand position is marked black. The last Asp uses both oxygen atoms from the mainchain
carbonyl and side chain carboxyl as the calcium ligand atoms
22 CALCIUM-BINDING PROTEINS
receptor (PLA2R), Endo180/uPARAP, and DEC-205/gp200- interaction with carbohydrates is independent of calcium
MR6/CD205. The first three contain eight CTLDs and the last binding.172
one contains ten.172
The mannose receptor subfamily members contain an
N-terminal Cys-rich domain that provides an additional 4.4.3 Selectins (CD62)
sugar-binding site, a fibronectin type-II domain that binds Selectins are cell-adhesion molecules that mediate leuko-
to collagen, the repeated CTLDs, a transmembrane segment, cyte recruitment in immune reactions and signal transduction.
and an intracellular tail that interacts with the cytoplasmic Selectins comprise three members termed E-, P-, and L-
proteins. The CTLD4 and 5 instead of the CTLD at selectin. The CRD is located at the N-terminus, followed by
the end of the mannose receptor are the most critical an EGF-like domain. There are various numbers of consensus
domains for calcium binding and sugar binding. Endo180 repeat sequences following the EGF-like domain. P-selectin,
has also been demonstrated to bind monosaccharides. L-selectin and E-selectin contain nine, six, and two repeats,
However, CTLD5 within M-type phospholipase A2 receptor respectively. A transmembrane segment and a cytoplasmic
mediates protein protein interactions instead of protein-sugar tail are located at the C-terminal. The key domains for target
interactions.172 recognition and sugar binding are the N-terminal CRD and
Figure 24(a) shows the structure of mannose receptor EGF-like domain.167,176
CTLD4 (1EGG),173 which shares a mechanism of calcium- The CRD of selectins is similar to that of MBL, or MBP.
mediated sugar binding that is similar to that in MBL-A. As shown in Figure 24(b), selectins do not have the Ca1
The same sequence pattern for Ca2 binding in MBL-A binding site of MBL-A. However, crystal structures of E-
is conserved in the mannose receptor CTLD4. As shown selectin (1ESL)174 and P-selectin (1G1Q, 1G1R, 1G1S, and
in Figure 23, mannose receptor CTLD4 has all of the 1G1T)177 have revealed that the principal calcium-binding
five conserved ligand residues for calcium binding except site mediating sugar binding (Ca2) is conserved. Similar to
Glu-733. Glu-733, corresponding to Glu-193 in MBL-A, the mannose receptor, selectins contain the five conserved
is replaced by the side chain carbonyl of Asn-728. This residues of the Ca2 binding pattern of MBL-A but only four
Asn is not conserved in CTLD-5; instead it contains a of them bind to calcium. Glu-88, corresponding to Glu-193
conserved Glu-residue corresponding to Glu-733. The bound in MBL-A, is not used for calcium binding. The bound sugar
sugar provides an additional two oxygen atoms for Ca2. provides additional ligands for this calcium.174,177
The Ca1 binding site is clearly different from the mannose
receptor and MBL-A. In the mannose receptor CTLD4, Asn-
728, Asn-731, Glu-737, and Asn-750 coordinate to Ca1.173 4.4.4 Asialoglycoprotein Receptor
Both CTLD1 and CTLD2 of Endo180 have the conserved The hepatic ASGPR is involved in receptor-mediated
calcium-binding pattern as observed in MBL-A. However, endocytosis via coated pits. It is a hetero-oligomeric protein
the M-type phospholipase A2 receptor and DEC-205 do with two subunits of H1 and H2. ASGPR contains multiple
not have this conserved calcium-binding pattern and their CRDs and specifically binds to oligosaccharides in glycans.178
The structure of the CRD of H1 subunit (1DV8)175 is
shown in Figure 24(c). There are three bound calcium ions,
two of which are similar to the Ca1 and Ca2 in MBL-A. As
shown in Figure 23, the calcium-binding pattern of Ca2 in
MBL-A is almost conserved in ASGPR CRD, including the
E-11x-N-D sequence and the shared Glu ligand with Ca1.
The differences include the change of E-x-N sequence at
the N-terminus of the loop to Q-x-D, which is critical for
galactose selectivity in ASGPR. Further, the distance between
this calcium binding sequence to the shared Glu increases to
10 residues. The protein ligands for Ca2 are Gln-239, Asp-
241, Glu-252, Asn-264, and Asp-265 (main chain and side
(a) (b) (c)
chain). Ca1 in ASGPR contains four of the five Ca1 ligands
of MBL-A. It is coordinated by Asp-215 (bidentate), Asp-
Figure 24 (a) The structure of CTLD4 of mannose receptor 242, Glu-252 (bidentate), and Asp-253. ASGPR has a Pro at
(CTLD4, 1EGG)173 with two bound calcium ions. (b) The structure the corresponding position of Glu-165 in MBL-A. The third
of CRD (dark red) and EGF-like domain (light colored) of E-selectin calcium ion is unique to this protein. It is coordinated mainly
with the functional calcium (green) (1ESL).174 The two nonspecific by two glutamate residues, Glu-196 and Glu-227, both of
bound calcium ions are shown in lighter color. (c) The structure of
the CRD on H1 subunit of ASGPR with the two calcium ions (green) which provide their two carboxyl oxygen atoms as bidentate
as in normal C-type lectin (1DV8).175 The third calcium ion unique ligands. The additional ligands come from the mainchain
to this protein is in orange carbonyl of Val-190 and water.175
CALCIUM-BINDING PROTEINS 23
4.4.5 NK Receptor and Other C-type Lectins GBP is located 63 residues away from the primary sequence
(Figure 25).180
Natural killer (NK) receptors are a group of proteins
expressed at the surface of NK cells.167,179 They share
some common features including the transmembrane domains, 4.5 The Extracellular Calcium-sensing Receptor
intracellular tails, the formation of homodimers, and the C- The extracellular calcium-sensing receptor (CaR) is a
terminal CTLD. There are many members, such as Ly49, detector for the concentration of extracellular calcium in
CD69, and NKG2, in the family of NK receptors. These blood and extracellular fluid.181184 It is responsible for
proteins have reserved the hydrophobic pattern of the C-type calcium homeostasis. In this case, calcium functions as
lectins such as MBL but lack the conserved calcium-binding a first messenger to activate CaR outside cells. This
residues. Many of them have been shown to function activation of CaR has several major signal transducing effects.
calcium-independently.167,179 More and more C-type lectins First, it activates phospholipase C (PLC) to generate the
have been discovered as a result of the fast progress in second messengers of diacylglycerol (DAG) and inositol
the field. For example, tetranectin and type-II antifreeze triphosphate. Second, it inhibits adenylate cyclase to reduce
proteins are found to be C-type lectins that partially share intracellular cyclic AMP concentration. It can also regulate
the calcium-binding geometry and calcium-binding pattern nuclear function by activating the mitogen-activated protein
of MBL. kinase pathway. Hofer et al. have shown that the CaR
mediates intercellular communication that allows cells
to be informed of the calcium-signaling status of their
4.4.6 Galactose-binding Protein neighbors.183
The CaR is expressed in many cells such as parathyroid
Galactose-binding proteins contain a unique calcium-
cells and C cells in the thyroid gland. It is also expressed
binding site that differs from the general C-type lectins.
in the kidneys, osteoblasts, in the gastrointestinal mucosa,
GBPs are not classified as C-type lectins because calcium
and hematopoietic cells in bone marrow. It has been found
binding is not required for their biological function. Figure 25
that CaR is expressed in different amounts on the cell
shows the three-dimensional structure of the galactose-binding
face of many cell types and in diverse species. CaR is a
protein.180 The calcium-binding geometry of the GBP is very
member of the G protein-coupled receptor family with seven
similar to that of EF-hand motif although it is not completely
hydrophobic transmembrane helices in the plasma membrane.
formed by a continuous calcium-binding loop flanked with It has a large N-terminal domain with about 600 amino acids
both helices. The first four ligands of GBPs are the same as located in the extracellular environment and is essential for
EF-hand proteins with the calcium-binding pattern D-x-N/D- sensing extracellular calcium concentration. CaR has a large
x-D/N-x-Mainchain-x. A water-mediated ligand of Glu/Gln is cytosolic C-terminal domain with about 200 amino acids
also located at loop position 9. The bidentate Glu (E203) of the that is subjected to phosphorylation. A dimeric structure has
been proposed based on the known crystal structure of the
metabotropic glutamate receptor type 1.
Q142 E205 Calcium pumps, also termed Ca2+ -ATPase, are calcium
channels that transport calcium from the low concentration
cytoplasm to the high concentration extracellular space or
ER/SR lumenal side using the energy of ATP hydrolysis.
Q140 D134 Based on their locations, calcium pumps are classified into
two groups, plasma membrane Ca2+ -ATPase (PMCA) and
sarcoplasmic reticulum Ca2+ -ATPase (SERCA).185187 Four
N136
D138 basic isoforms of PMCA (PMCA1 4) have been identified
(a) (b) and the other PMCA isoforms are the alternative splicing
products of the basic isoforms. PMCA1 and 4 are ubiquitously
expressed in different tissues and PMCA2 and 3 are expressed
Figure 25 (a) The structure of GBP (1GLG)180 with the cal- in nerve cells. Three basic isoforms of SERCA pump and
cium-binding in green and the sugar-binding site in pink. (b) The
local view of the calcium-binding site of galactose-binding pro- several splicing variants have also been identified.185
tein with ligand residues labeled. The calcium-binding geometry of Both PMCA and SERCA have ten TMS. Several
galactose-binding protein is very similar to that of EF-hand motif loops are exposed to the extracellular space or the inner
24 CALCIUM-BINDING PROTEINS
SR/ER lumen. The major parts of the proteins exist in to form the stalk. Calcium-binding sites are located in these
the cytoplasmic solutions to form functional units.185187 transmembrane domains. The first calcium ion is coordinated
The PMCA cytoplasmic part comprises four units: the N- by Asn-768 and Glu-771 on TMS-5, Thr-799 and Asp-800
terminal unit, the acidic phospholipids binding unit, the on TMS-6, and Glu-908 on TMS-8. The second calcium ion
ATP-binding unit that contains the catalytic aspartate that is binds with the side chain of Glu-309 at TMS-4, Asn-796
phosphorylated during the pumping process, the nucleotide- and Asp-800 at TMS-6 and the mainchain carbonyl of Val-
binding domain containing the ATP-binding motif and a 304, Ala-305, and Ile-307 at TMS-4. The phosphorylation
fluorescein isothyocyanate (FITC) binding site, and the position that triggers the calcium transportation is located at
C-terminal regulation unit that contains the sites for PKA, Asp-351 in a very conserved sequence of DKTGT, about
PKC, calmodulin, and calcium binding. The calmodulin 40 A away from the calcium-binding sites.190 A series of
binding inhibits the protein function. SERCA comprises the conformational changes are required to mediate these two
first three units similar to PMCA but lacks the long C-terminal separated calcium binding and phosphorylation effects and to
sequence. Each ATP is used to pump one calcium ion out of make them function together.
the cytoplasm by PMCA and two calcium ions into SR/ER The structure of the E2 state (1IWO) has also recently been
lumen by SERCA. Two protons are exchanged from SR/ER solved by stabilizing the conformation in the calcium-free form
lumen to cytoplasm at the same time by SERCA.185187 using thapsigargin (TG).191 Consistent with the EM results, a
Before 2000, structural information, especially the topology large conformational change has been observed compared to
of the pumps was mainly from electron microscopy, structural the E1 state. Although the individual cytoplasmic units do not
modeling and low resolution X-ray crystallography.188 Upon exhibit significant structural change, the overall arrangement
the binding of calcium, a large rearrangement of the of these units is altered. The N-terminal unit rotates about
cytoplasmic units has been observed. A simple model has 110 and the phosphorylation domain rotates about 30 with
been proposed for this observation. The model postulates the respect to the membrane plane. The nucleotide binding unit
existence of two conformations E1 and E2. While in the E1 rotates 50 further with respect to the phosphorylation unit.
state the protein has high affinity calcium-binding sites and This reorientation results in a relatively compact structure in
upon phosphorylation the conformation changes to E2 that has contrast to the relatively open structure in the E1 state.191
low affinity sites.185,189 The first high-resolution structure of This conformational change also causes the rearrangement
a P-type ATPase, that of the Ca2+ -ATPase of skeletal muscle of the calcium-binding ligands, such that those at TMS-6
sarcoplasmic reticulum, was published in 2000.190 A clearer rotate 90 and TMS-4 shifts down 5 A.190,191 Unlike the
picture comes from the X-ray structure of SERCA1 protein previous postulation that in the E2 state the calcium-binding
at the E1 state (1EUL) (Figure 26).190 Ten TMSs are almost sites face the SR lumen, the calcium sites in this model
entirely helical with four of them extended into the cytoplasm face the cytoplasm in both states. The detailed pathway
(a) (b)
Figure 26 The structures of SERCA at the E1 state (a, 1EUL)190 and E2 state (b, 1KJU)191 are shown. The light blue lines represent
the phospholipid bilayer membrane. The phosphorylated domain and the ATP-binding domain are labeled as cyan and brown, respectively.
Calcium is represented as green ball
CALCIUM-BINDING PROTEINS 25
of calcium transportation has yet to be identified though Annexins play important roles in many cellular processes
some important residue locations (e.g. Glu-309) have been by binding negatively charged phospholipids in a calcium-
proposed.186,190,191 dependent manner. As a molecule that binds and aggregates
In contrast to SERCA, the Ca2+ release channel of the SR phospholipid vesicles, it frequently accompanies vesicle or
(RyR) transports calcium from SR to cytoplasm following membrane fusion. Annexins were shown to be important in
the calcium gradient with no specific energy required. RyR membrane organization, membrane transportation, exocytosis
has three isoforms. They are activated by low concentration (annexin A1, A2, A3, A6, A7, A11, A13, and B7), endocytosis
of calcium, adenine nucleotide, and cADP and are inhibited (annexin A1, A2, and A6), and phagocytosis (annexin A1 5,
by a high concentration of calcium. Other factors include A7, and A11). Annexins A7 and A5 and annexins A2
calmodulin, which is involved in the regulation of RyRs. The and A4 regulate calcium and chloride channel activities,
protein forms a tetrameric structure and looks like a square respectively.198 In addition to calcium and phospholipids,
prism with several pores.192 IP3 R (inositol 1,4,5-trisphosphate several proteins, such as EF-hand proteins S100A6, S100A10,
receptor) is another calcium release channel that transports S100A11, and sorcin, and cytoskeletal protein actin, have been
calcium from ER/SR into cytoplasm. IP3 R is regulated directly identified as interacting with annexins. S100 EF-hand family
by IP3 together with the cytoplasmic calcium concentration members S100A6, S100A10 and S100A11 specifically bind
and CaM binding.193 to annexins A11, A2, and A1, respectively. Sorcin binds to the
The other calcium channels that regulate cytoplasmic GYP-rich N-terminal tail of annexin A7. Several annexins,
calcium concentrations include Na+ /Ca2+ exchanger and such as A1, A2, A5, and A6, interact with actin. Other proteins
H+ /Ca2+ exchanger. Instead of using the energy from ATP associated with annexin include phospholipase A2, p120 Ras
hydrolysis, the sodium or proton gradient across the membrane GTPase activating protein (GAP), protein kinase Fyn and
is used to transport calcium. Nine TMS segments and one Pyk2, and so on, suggesting annexins are involved in many
large cytoplasmic sequence between TMS-5 and TMS-6 more biological activities that have yet to be explored.198
are predicted in classical Na+ /Ca2+ exchanger. There is no The number of X-ray and NMR structures of annexins
detailed structural information about these families of proteins. exceeds 40, including 23 of annexin A5. Recently, calcium-
The calcium-binding sites are proposed to be located in the independent phospholipid binding of annexin has been
cytoplasmic sequence.187,194 revealed. Instead of binding calcium, lowering the pH
Voltage-gated calcium-channel and receptor-gated calcium also causes annexin A5 and B12 to interact with the
channel are two channels that have the reverse effects of lipid membrane.
PMCA. They transport the calcium influx following the All annexins are composed of two principal domains, the
calcium gradients regulated directly by the electric potential conserved C-terminal core and the N-terminal tail unique to
between the two sides of plasma membrane or receptor their subfamily. The length of the N-terminal tail is shorter
binding, respectively.193 than 40 residues in most of the annexins with the exception of
the A7 and A11 subfamilies, which have up to 160 and 195
residues, respectively. The current known protein protein
interaction with annexin occurs at the N-terminal tail. The
diversity of this small N-terminal tail contributes at least
6 MEMBRANE CALCIUM-BINDING PROTEINS: partially to the diversity of annexin functions.195,198
ANNEXINS AND C2 DOMAIN Almost all annexins contain a core domain with four
subdomains, each with about 70 residues, with the exception
of A6 that has eight repeats (Figures 27 and 28).195,196,198200
6.1 Annexin Calcium and lipid binding sites are located at the core domains.
As shown in Figure 27, the core domains of A5 are composed
Annexin is a family of calcium-binding proteins that bind of four repeated subdomains. X-ray crystallography has shown
phospholipid. More than 160 members of this family have been that the repeated subdomain contains five -helices. Two
identified. Based on their sources, annexins are classified into calcium-binding helix-loop-helix motifs (A/B and D/E) are
five groups. Group A is typically thought to be in vertebrate arranged as a four-helix bundle. Helix C crosses over the
animals, but studies after 1990 show some of the Group bundle to hold the two helix-loop-helix structures in the
A annexins appear in invertebrates. It is one of the most bundle together. The four repeat segments of the annexin core
frequently studied groups of annexins. To date, 13 subfamilies form a planar cyclic structure, in which subdomain 1 interacts
in Group A with different N-terminal tails have been identified. with subdomain 4 and all the bundles are lined up in the
Group B is represented in nonvertebrate metazoans. Groups same orientation, resulting in a hydrophilic pore similar to
C, D, and E are annexins in Mycetozoa and fungi, plants, the ion channels. However, the monomeric annexins are not
and protists, respectively. Annexin overall is an intracellular proposed to be ion channels because of the hydrophilic surface
protein, but it has also been found in the extracellular matrix of the helices and the relatively shorter length of the -helices
(e.g. annexin A1).195198 for spanning through the bilayer membrane.198,199 The X-ray
26 CALCIUM-BINDING PROTEINS
(a) (b)
Figure 27 (a) A pore is formed by the four repeated domains of annexin A5 (1A8A)199 in which the domain I (light blue) interacts with
domain IV (orange) directly. (b) The structure of annexin A5 with four domains in which all calcium is bound to the top of the protein
structure of A6 shown in Figure 28 contains eight repeated D-helix may have to be switched to a conformation similar to
subdomains that form two regions, each with four domains as those in the other segments.198,201
in other annexins.200 As a protein located at the cytosolic side of the membrane,
Most of the crystallized structures of annexin contain the calcium-binding affinity of annexin is weak. In vitro
different numbers of calcium or lanthanide ions. The calcium measured apparent dissociation constants of calcium are from
binds at the AB loop and/or the DE loop in each repeated micromolar to millimolar. Annexins appears to be apo-form
segment. For example, in annexin A5, the AB-loop calcium- at the submicromolar intracellular calcium concentration.
binding site comprises three mainchain carbonyl ligands at Given the fact that the function of annexin is calcium-
the AB-loop and two side chain carboxyl ligands from one required in vitro, it is plausible to propose that annexin acts
bidentate Asp or Glu-residue at the DE-loop. Two solvent differently in vivo. Either the in vivo function of annexin is
molecules are used to obtain the pentagonal bipyramidal calcium independent (less likely), or, more likely, in vivo,
geometry. The calcium-binding site at the DE-loop comprises by interacting with membrane or target protein ligand, the
two mainchain ligands at the DE-loop and two ligands from calcium-binding affinity of annexin increases owing to the
one bidentate acidic residue at E-helix. Up to three solvent environment change. In addition, the calcium concentration
molecules are used in this site.198,199 near the membrane region may be higher than the average
The conformational change induced by calcium binding in level in the cytosol.198
annexin is relatively small. The largest change that has been
detected is the repacking of the repeated segment III D-helix
in annexin A1. The X-ray structure shows that without the 6.2 C2 Domains
calcium binding the N-terminal tail of A1 forms an -helix and
The C2 domain was first identified in calcium-dependent
replaces the position of the D-helix of segment III, while the
PKC isoforms, and refers to the conserved domain 2 in PKC
D-helix is unwound and partially points out. With the calcium
with about 80 160 residues. To date, more than 100 proteins
binding, the tail may have to be out of the core domain and the
have been identified as containing C2 domains. It is one of the
most widely used modules of intracellular calcium-binding
proteins. Some proteins contain two or more repeats of the
C2 domain in a single peptide chain, such as synaptotagmin,
double C2 protein (DOC2), and Munc13.202,203
The structural information of C2 domain is primarily from
the studies on PLC, PKC, cPLA2 (cytoplasmic phospholipase
A2), factors, and synaptotagmin (Figure 29). Synaptotagmin
I contains two C2 domains, C2A and C2B, of which C2A
is the first C2 domain with a solved structure. Currently,
more than twenty structures of C2-domain-containing proteins
have been obtained by X-ray and NMR. The C2 domain
contains eight -strands that form a compact -sandwich
structure composed of two layers with four strands in each
layer.202,203 Based on the topology of these -strands, they
are classified as type I and type II C2 domains. In type I
Figure 28 The structure of Annexin A6 (1AVC)200 with eight C2 domains, such as synaptotagmin and DOC2, -strands
repeated domains in different colors 1, 2, 5, and 8 are in the same layer and -strands 3, 4, 6,
CALCIUM-BINDING PROTEINS 27
ions (termed Ca1 3) are bound to five Asp, one Ser, and
three mainchain carbonyls located at loop 1 and loop 3.
Of these ligands, Asp-172 and Asp-230 are shared by Ca1
and Ca2, Asp-238 is shared by Ca2 and Ca3, and Asp-
232 is shared by all three calcium ions. The mainchain
carbonyl from Leu-171 binds only to Ca2, an Asp-178 side
chain and Phe-61 mainchain bind to Ca1, and Ser-235 side
chain and Lys-236 bind to Ca3. The substrate phospholipids
have been proposed to provide additional ligand atoms to
the pentagonal bipyramidal geometry of the calcium-binding
sites. In the absence of phospholipids, the calcium dissociation
constants of synaptotagmin I C2A domain are low (0.06 mM to
>1 mM), a value too weak to bind calcium at the intracellular
environment.203205
The calcium binding in PLC1 C2 domain revealed by x-ray
crystallography has two similar and one distinct site compared
(a) (b) to synaptotagmin I. The locations for Ca1 and Ca2 are almost
the same, while the ligands for these two calcium ions, Asp-
653, Asp-706, Tyr-707, Asp-708, and Asp-714 correspond
to Asp-178, Asp-230, Phe-231, Asp-232, and Asp-238 in
synaptotagmin I, respectively. The ligands corresponding to
Leu-171 and Asp-172 are missing. The ligands corresponding
to those for Ca3 are retained and have similar orientation
in PLC1 but no calcium occupies the pocket. The third
calcium in PLC1 shares one ligand residue with Ca1 (Asp-
653, bidentate in this site) and uses the other three ligands
from loop 1 and loop 2 (Asn-677, Ser-650, and Ile-651).
Like synaptotagmin I, the additional ligands for pentagonal
bipyramidal geometry may come from the target molecule
phospholipid.
C2 domain represents a large family of proteins with
different functions.204,208 Most of them bind calcium and
phospholipids. Most members of the C2 domain protein fam-
(c) ily are involved in signal transduction, such as PKC and PLC
(phosphoinositide-specific phospholipase C), or membrane
Figure 29 (a) The C2 domain in cPLA2 (1RLW)205 has type II
traffic, such as synaptotagmin and rabphilin-3.202,203 To date,
topology, in which the -strands 7, 8, 1, and 4 (light blue, left to several important subfamilies have been extensively studied
right) form one layer while the -strands 6, 5, 2, and 3 (yellow, and their functions are relatively clear. First, the classical PKCs
left to right) form another layer in the -sandwich structure. (b) The (isoforms , , and ) contains type I C2 domain, and some
C2 domain in PKC (1A25)206 has type I topology, in which the of the non-classical PKCs (, , , and ) and yeast PKCs con-
-strands 8, 1, 2, and 5 (light blue, left to right) form one layer and
the -strands 7, 6, 3 and 4 form another layer. (c) The C2 domain tain type II C2 domains. In classical PKCs the C2 follows the
(blue) in the -toxin (1QMD)207 is shown. The calcium ions in all C1 domain while for the nonclassical PKC, the C2 domain is
three figures are labeled green and the other metal ions (Zn in -toxin before the conserved C1 domain. This family of protein kinases
and Cd in PKC) are labeled gray plays important roles in the cell signal transduction pathway by
mediating protein phosphorylation. The biological functions
of these C2-containing PKCs with a proper calcium-binding
and 7 are in the other layer. In type II C2 domain, such pocket are calcium-dependent. Calcium-independent C2-
as cPLA2 and PLC, the -strands 1, 4, 7, and 8, and 2, containing PKC does not contain conserved calcium-binding
3, 5, and 6 are in two layers, respectively.202,203 Loops ligand residues.203,206,209211 Second, cytosolic phospholipase
connecting the -strands are located at the two ends (top A2 (cPLA2) cleaves arachidonic acid from glycerophospho-
and bottom) of the protein. Two or three calcium ions bind lipids using the C-terminal catalytic domain. The C2
to the loop regions located at the top of the protein. The domain at the N-terminus interacts with neutral phospholipid
ligand residues of the calcium-binding sites in C2 domain vesicles containing phosphotidylcholine or phosphotidyl-
are widely separated in the primary sequence.202,203 In the X- ethanolamine through a calcium-dependent mode to localize
ray structure of synaptotagmin I C2A domain, three calcium the cPLA2 to its target membrane substrate. The C2 domain
28 CALCIUM-BINDING PROTEINS
in cPLA2 is of type II topology. Four of the five aspartate manner. Some known synaptotagmin target proteins include
ligands in synaptotagmin I are retained in cPLA2 and the fifth clathrin-AP2, syntaxin, and PKC and so on. The oligomer-
is mutated to asparigine.203,205,212 Third, phosphoinositide- ization of synaptotagmin is also calcium dependent.203,205,219
specific phospholipase C (PLC) liberates inositol trisphosphate Eighth, double C2 (DOC2) protein plays a role in regulating
(IP3) and DAG when activated. Both IP3 and DAG are calcium-dependent exocytosis, particularly in vesicle cycling
directly involved in the regulation of intracellular functions in response to stimuli or phorbol esters (PE). It comprises
(e.g. IP3 regulates several calcium channels and DAG regu- two type I topology C2 domains and a Munc13 interacting
lates several PKC isoforms). The C2 domain in PLC is of type domain (MID). DOC2 is localized to a pre-synaptic vesicular
II topology. It facilitates the catalytic domains interaction terminal. It interacts with other exocytotic proteins including
with the substrate. PLC also contains an EF-hand calcium- the presynaptic PE receptor Munc13-1, syntaxin-interacted
binding domain and a pleckstrin homology(PH) phospholipid protein Munc18, and dynein component Tctex-1. The DOC2-
binding domain.203,208,213 Fourth, -toxin is a eukaryotic phos- Munc13 complex is required for vesicle maturation in certain
pholipase C, which is capable of binding to mammalian glutamatergic synapses.220 Munc13 comprises two type II
cell membrane and cleaving membrane-bound phosphatidyl- C2 domains, one type I C2 domain, and one C1 domain.
choline (or sphingomyelin) to produce phosphocholine and It is expressed in neuronal cells and functions cooperatively
DAG (or ceramide). X-ray crystallography has revealed three together with DOC2 in regulating exocytosis and neurotrans-
calcium ions in the C2 domain of alpha toxin. Unlike the synap- mitter release process.203,220 Ninth, rabphilin-3A is identified
totagmin or PLC, the three calcium ions are clustered but only as a protein that interacts with Rab3A, a small ras-related
share one ligand (Asp-298) that interacts with Ca2 with the side membrane-bound GTPase playing a role in neurotransmit-
chain carboxyl group and with Ca3 with a main chain carbonyl ter release and exocytosis, in the GTP-bound form. Other
group. The ligands for Ca2 are located continuously (Asp-293, partner proteins such as Rab27 have also been observed for
Asn-294 main chain, Gly-296 main chain, and Asp-298) while rabphilin. The Rab3A-binding domain is at the N-terminal
the ligands for Ca1 (Asp-269 main chain, Gly-271 main chain, and two type I topology C2 domains are at the C-terminal of
Asp-336, Ala-337 main chain, and Glu-32) and Ca3 (Thr- rabphilin-3A. The C2 domains of rabphilin-3A interact with
272 main chain, Asp-273, Asn-297, Asp-298 main chain) phosphatidylserine in the presence of calcium. The C-terminal
are discontinuous.207,214 Fifth, phosphatidylcholine-specific C2 domain is critical for secretion functions of rabphilin-3A.
phospholipase D (PLD) catalyzes the cleavage of phospho- Mutations in this domain will impair calcium-dependent vesi-
lipid to produce phosphatidic acid and a free head group such cle binding.221,222 Tenth, several GAP have been identified
as choline. The putative calcium-binding ligands in the C2 as having a C2 domain, including p120-rasGAP, GAP1m,
R-Ras-GAP, BCR, ABR, and BUD2. The C2 domain of
domain of PLD are diverse in different isoforms. The apparent
p120-rasGAP binds phosphotidylserine and phosphotidylinos-
calcium-binding affinity without substrate of PLD, , and
itol in the presence of calcium. Functionally, p120-rasGAP
varies more than two orders of magnitude.215 Sixth, phos-
down-regulates the mitogen-activated protein kinase pathway
phatidylinositol 3-kinase (PI3K) and PTEN catalyze reverse
after epidermal growth factor stimulation and also regulates
reactions on phosphorylation and dephosphorylation of phos-
cell proliferation.223 Eleventh, human coagulation factors are
phoinositides. The isoforms PI3K , , and VPS34P have a
essential for blood clotting through a thrombin-mediated
type II C2 domain while isoform PI3K 68D has a type I C2
mechanism. Factor V and VIII share a similar sequence and
domain. The calcium-binding ligands in PI3K C2 domain are
topology. They are each represented by the domain structure
not complete. The functions of PI3K and PTEN as a tumor
A1-A2-B-A3-C1-C2 and share 40% sequence homology in the
suppressor are not dependent on calcium.203,216,217 Seventh,
A and C domains. After cleavage by thrombin or factor X, the
synaptotagmin is a family of transmembrane proteins with domains A3, C1, and C2 form the light chain. The C2 domain
two type I C2 domains in the cytosol. It is involved in vesi- in factors V and VIII is critical for mediating the membrane
cle fusion and exocytosis events in the cell.218 Synaptotagmin binding of proteins.224226 With the increasing number of C2-
I V, X, and XI are expressed in the neuron system and the oth- containing proteins, the C2 domain has become one of the most
ers (VI IX) are expressed in other tissues. The C2A domain popular domains in nature. In addition, the currently known
binds with calcium and triggers calcium-regulated exocytosis C2 domain members also include perforin, phosphatidylserine
and secretion. The C2B domain of synaptotagmin I and II decarboxylase, SCH9 kinase, RSP5, Ege A, and so on.
binds inositol high polyphosphates and inhibits the exocytosis
and secretion by this binding. Synaptotagmin I is also known to
be crucial for neurite outgrowth. Synaptotagmins are involved
in constitutive vesicular trafficking in addition to regulated 7 CALCIUM-BINDING PROTEINS IN
exocytosis. The C2B domain of synaptotagmin III, V, VI, ENDOPLASMIC RETICULUM AND
and X lacks the inositol high polyphosphate,for example, IP4, SARCOPLASMIC RETICULUM
binding ability resulting in the deficiency of IP4 inhibition.
C2 domains in synaptotagmins also mediate protein protein ER and SR are the major calcium stores in the cell
interactions through a calcium-dependent or independent (Figure 1). They play a vital role in regulating cell functions.
CALCIUM-BINDING PROTEINS 29
With the proper stimuli, calcium in the ER/SR is released to the folding of the CSQ. The calcium-loaded CSQ is dimerized and
cytoplasm activating calcium-signal proteins. To restore the then polymerized to form a long chain, which further allows
rest state of the cell, calcium is pumped out of the cytoplasm even more calcium to be bound intermolecularly. The lined
by PMCA, SERCA, and Na+ /Ca2+ exchanger. Most of the CSQ cooperates with the calcium release channel of SR/ER
calcium ion in ER is buffered by many lumenal calcium- in regulating the cytoplasmic calcium concentration.227
binding proteins such as CSQ, calreticulin and calnexin. There After more than 10 years of attempting to crystallize CSQ, it
are other calcium-binding chaperone molecules in the ER was finally accomplished with 0.3 M K+ in the absence of Ca2+
such as grp94, PDI family, and BiP. These proteins are more (1A8Y).231 The solved x-ray structure of CSQ contains three
likely to chaperone the non-glycoproteins. One member of the structurally similar domains of a thioredoxin fold although
protein disulfide isomerase (PDI) family, ERp57, cooperates there is no significant repeat sequence in the primary structure
with calreticulin and calnexin.227229 (Figure 30). Each thioredoxin-like domain comprises a core
that is formed by five -strands and four surrounding -
helices. The interior of the core is mainly composed of
7.1 Calsequestrin (CSQ) hydrophobic residues. The bulky content of acidic residues is
CSQ is the major buffer protein in the lumen of the SR located at the -helices and the connecting loops. Ca2+ ions
of muscle cells, especially those bound at the calcium release bind to the protein surface and the spaces between domains
channel, the ryanodine receptor, and through junction and (Figure 30).231 CSQ monomer can associate in front to front
triadin. CSQ was shown to determine the functional size and and back to back chains to create additional calcium-binding
stability of cardiac intracellular calcium stores.230 As shown sites in clefts between the individual molecules. These two
in Figure 30, more than 1/3 of the total residues of CSQ distinct dimerization contacts in CSQ crystals suggested a
are glutamate or aspartate (a total of 110 carboxylate groups) mechanism for Ca2+ regulation resulting from the occurrence
residues.231 One CSQ molecule is capable of absorbing 40 50 of coupled Ca2+ binding and protein polymerization.232
calcium ions with an average calcium-binding affinity of
about 0.6 1 mM. All calcium or metal binding ability is 7.2 Calreticulin and Calnexin
mainly determined by the charge charge interaction without a
defined calcium-binding pocket. The calcium binding of CSQ Calreticulin functions as a chaperone protein for the folding
has both high on-rate (109 M1 s1 ) and off-rate (106 s1 ), of newly synthesized proteins and glycoproteins.229,233 It is
which allows this protein to release and bind large quantities also a major calcium-buffer protein residing in the lumen
of calcium rapidly. Owing to the highly negatively charged of the ER. Calnexin exhibits a high degree of similarity
surface, calcium or monovalent cation ions are required for the to calreticulin in primary sequence and structure. It also
has functions similar to calreticulin such as calcium binding
and recognition of misfolded proteins. The major difference
between these two proteins is that calreticulin is able to
move in the lumen of the ER while calnexin is an integral
membrane protein of the ER, interacting transiently with its
protein folding intermediates at the stationary phase. Both
proteins bind to the monoglucosylated carbohydrate of the
glycoproteins. Misfolded non-glycoproteins may also bind to
calreticulin and calnexin.229,234,235
Both calreticulin and calnexin comprise three domains: a
globular N-domain, an extended proline-rich P-domain, and
a transmembrane helix in calnexin or an acidic calcium-
binding C-domain in calreticulin.229,236 The structures of the
soluble part of calnexin and the P-domain of calreticulin
have been reported. The crystal structure of calnexin (1JHN)
shows an unusual structure in that the P-domain extends
far away from the N-domain like an arm (Figure 31). The
glycoproteins interact with the N-domain surface facing the
arm. A calcium ion binds to the N-domain using the ligands
from the carbonyl of Ser-75 and the carboxyl of Asp-118
and Asp-437 (bidentate).236 The P-domain (residue 189 288)
NMR structure of calreticulin (1HHN, 1K91 and 1K9C) is
very similar to that of calnexin.237,238 This structure shows an
Figure 30 The structure of CSQ (1A8Y)231 with acidic residues extended hairpin topology, with three short antiparallel beta-
highlighted in red sheets, three small hydrophobic clusters, and one helical turn
30 CALCIUM-BINDING PROTEINS
(a)
(c)
(b)
Figure 32 (a) The structure of -lactalbumin with calcium (green ball) and an additional Zn (gray ball) binding (1HML).32 (b) The structure
of classical lysozyme (1LZ1) without the calcium-binding ability.57 (c) The structure of calcium-binding echidna lysozyme (1JUG)244 with
calcium binding. All these proteins have similar structures with a flanking loop (orange) located between the -domain (light blue) and the
-domain (purple)
ligand residues (Figure 32). In addition, the charge and surface of antibody binding or substrate binding complexes. The
electric potential of -LA and most of the lysozymes are available calcium-binding lysozyme includes X-ray structures
different. -LA is an overall acidic molecule and lysozyme of canine lysozymes 1EL1 (holo-form) and 1QQY (apo-
is basic. As shown in Figure 4, bovine -LA has a strong form), NMR solution structure of canine lysozyme 1I56,
negatively charged surface while noncalcium binding protein X-ray structures of equine lysozyme (2EQL, apo-form) and
human lysozyme has a strong positively charged surface. echidna lysozyme (1JUG, holo-form).
Typical lysozymes also do not have a molten globule state X-ray structures of apo (1F6R, bovine) and calcium-loaded
during the unfolding process.245249 (1F6S, 1HFY, bovine; 1A4V, 1B9O, human; 1ALC, baboon;
To understand the difference between -LA and typical 1HFZ, 1FKQ, 1FKV, 1HMK, goat; 1HFX, guinea pig) -
lysozymes, tremendous work has been done, including LA are available. The structures of zinc and manganese
peptide analogues, mutagenesis studies, and computational loaded -LA are also solved (1HML for zinc and 1PZY for
simulations. The calcium-binding loop and the following helix manganese). There are also solution NMR structures (1CB3,
of -LA have been transported into lysozyme individually or human) and complexes with substrate or galactosyltransferase
simultaneously. By introducing the Asp residues at the key (1NF5, 1NKH, 1NMM, 1NQI, 1NWG, and 1PZY) in the
positions without the following helix, lysozyme gains the Protein Data Bank.
calcium-binding ability with a Kd at 105 M range but not the
ability to have a molten globule state. By introducing the helix
without the calcium-binding loop, lysozyme can also form the
molten globule state without the calcium-binding ability. By
introducing both, lysozyme gains both the structural properties 9 RELATED ARTICLES
of -LA.248
As one of the extensively investigated protein families,
hundreds of lysozyme structures are deposited in the Protein Alkaline Earth Metals: Inorganic Chemistry; Biominerali-
Data Bank, including wild type from different sources zation; Cation-activated Enzymes; Coordination Numbers &
and numerous mutants. Also available are the structures Geometries; Metal-related Diseases of Genetic Origin.
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Carbides: Transition Metal 2 STRUCTURE AND BONDING
+
+ Likewise, carbon-containing gases such as methane or
+
+ benzene can be utilized as well (equation 2).
pd
pd
dd + + Ti + CH4 TiC + 2H2 (2)
+ + +
+ + +
1 423 mRyd 2 620 mRyd 5 636 mRyd
The preparation of TiC, VC, NbC, TaC, Mo2 C, WC, and
the chromium carbides are important technical processes for
the production of carbide powders for hardmetals. Generally,
Figure 1 MO bonding scheme for TiC. (Ref. 14. Reproduced by the carbides are prepared by the reduction of oxides with
permission of Wiley, Inc.) carbon; only Mo2 C and WC are manufactured by reaction of
the metal powders with graphite or carbon black.
bonding. Figure 1 shows these MO schemes for bonding in Solid solutions of transition metal carbides and carboni-
TiC, which were obtained by calculating the electron densities trides, which also play an important role in the hardmetal
in the (100) plane just below the Fermi energy.14 The lower industry, can be advantageously manufactured by the simul-
part of the figure gives the schematic bond type indicating taneous reduction of oxide or oxide-carbide mixtures in the
pd (left), dd (middle), and pd (right) bonds. The ionic presence of carbon (equation 3).
contribution to the binding mechanism in transition metal
carbides originates from a net charge transfer from the metal TiO2 + WC + 3C (Ti,W)C + 2CO (3)
to the carbon atom.
The chlorides of the transition metals can also be employed
to obtain transition metal carbides (equation 4). This reaction
proceeds in the gas phase at temperatures above approximately
3 PREPARATION 600 C. Because transition metal halogenides are rather
volatile, this reaction is usually used for chemical vapor
Transition metal carbides can be prepared by direct deposition of carbide layers on solid substrates or to produce
combination of the elements, preferably as powder mixtures, carbide powders with very fine (submicron) grain sizes
at elevated temperatures. If the heat generated by the reaction (nanopowders). In the latter case, the nucleation of the
CARBIDES: TRANSITION METAL SOLID-STATE CHEMISTRY 3
carbide particles must proceed in the homogeneous gas phase. and measurement of the volatile combustion products CO2 or
CO. There are several methods whereby this analysis can be
ZrCl4 + CH4 ZrC + 4HCl (4) carried out:
The oxides of the transition metals can be reduced by carbon volumetrically by absorption of CO2 in alkaline solutions;
according to the following overall reaction (equation 5). by measurement of the change in electrical conductivity of
an alkaline solution resulting from the CO2 absorption;
TiO2 + 3C TiC + 2CO (5) by amperometric titration of a Ba(OH)2 BaCl2 solution
after absorption of the CO2 content;
Investigations of this reaction have revealed that there are by gas chromatographic analysis of the CO2 (and N2 )
usually several intermediate steps involving lower oxides and content of the carrier gas.
carboxides of the transition metals until the final product is
reached. Another process to produce coarse carbide powders
from oxidic prematerials makes use of calcium carbide and 4.2 Physical Analysis of Carbon
aluminum as the reducing agent. The heat generated by the
exothermic process must be sufficient to reach the reaction Since carbides are extensively used in spatially restricted
temperature, which should be high enough to obtain physical sizes (thin films, powder particles in cemented carbides),
separation of the molten slag and the reaction product. This microanalytical techniques of local carbon analysis are of
principle has been used to manufacture coarse WC powders special interest for sample characterization. Electron probe
from wolframite, a naturally occurring tungsten ore, according microanalysis (EPMA) is the most successful method for the
to the following overall reaction (equation 6). In order to obtain quantitative analysis of carbon when the lateral resolution
conditions under which the reaction becomes self-sustaining, needs not to be better than about 2 m.
aluminum chips and iron oxides are added to the mixture. The highest accuracy is obtained by the use of external or
internal standards and a wavelength-dispersive spectrometer.
FeWO4 + CaC2 + 2Al WC + Fe + CaO + Al2 O3 + C (6) Problems arise when the carbon atoms in the standard and
sample material are differently bonded. This leads to slightly
WC and Fe form a regulus from which WC can be separated different peak positions and peak shapes. Errors arising from
by an acid leach process (Macro process15 ). these effects can be either avoided by using the same type of
Coarse chromium carbide powders have been produced by carbide in standard and sample or by measuring the peak area
reducing Cr2 O3 with aluminum powder in the presence of rather than the peak height. Bastin and Heijligers18 worked
carbon (equation 7). out the area-peak-factor procedure, where the ratio peak area
to peak height, in XRD the so-called intregral intensity, is
3Cr2 O3 + 6Al + 4C 3Al2 O3 + 2Cr3 C2 (7)
determined for a given compound. After this function has
been obtained for a specific carbide and a specific microprobe
Large single crystals of transition metal carbides can set up (since the peak area and peak height are a function of
be prepared either by the floating zone technique16 or the spectrometer) relative to the standard, a simple peak height
by the auxiliary metal bath technique.17 The first process intensity determination of standard and sample is sufficient
uses an RF induction heating equipment to form a melted for quantitative carbon analyses.
zone in a presintered carbide powder rod of typically 1 cm In the preparation of standards, diffusional techniques are
diameter, which is slowly moved along the rod. The samples of special importance. Using such techniques diffusion layers
so obtained are typically 10 cm long rods containing single are formed. With a special modification by use of wedge-
crystals up to the size of ca. 1 cm. The auxiliary metal process type samples, these layers are broadened19,20 and are thus
takes advantage of the fact that the carbides can be dissolved better accessible for the microprobe.2123 The samples consist
at high temperature in liquid iron group metals (Fe, Ni, and of several diffusion bands because of the various phases in
Co) and are reprecipitated upon cooling in the form of large the respective carbide system. Usually, however, the samples
faceted crystals, which can be separated from the metal bath should be single phase and homogeneous in order to make
by an acid leach process.
chemical gross compositional analysis applicable. Only with
a comparison of different techniques a real standardization is
possible. Such transition metal carbide standards have been
made from the phases VC, NbC, TaC22 and Cr3 C2 .23
4 CHARACTERIZATION In addition, contamination of the analyzed surface by
hydrocarbons may coincide in the measurement. Therefore,
4.1 Chemical Analysis of Carbon anticontamination techniques such as using a cold-trap or an
oxygen jet should be applied.
Carbon analysis of transition metal carbides is nearly Relief effects owing to insufficient or inapplicable polishing
exclusively performed by combustion of the carbide in oxygen routines can be avoided by lapping of the specimens.21
4 CARBIDES: TRANSITION METAL SOLID-STATE CHEMISTRY
The free energy of formation of transition metal carbides 5.2.2 Group 5 Transition Metal Carbon Systems
does not change significantly with temperature. Hoch24 has
The group 5 transition metal carbon systems (Figure 3
derived interaction parameters between carbon and the metal
shows reinvestigated portions of their phase diagrams by
atoms in group 4 and 5 transition metal carbides from metal
means of diffusion couples, information at high temperature
and carbon vapor pressure measurements at high temperatures,
including the liquid phase can be obtained from the ASM
which quantitatively describe the partial free energy of carbon
Handbook25 ) are again very similar to each other and contain
within the homogeneity region of the monocarbides. From
structurally identical subcarbide phases -T2 C and -T4 C3x
these values it was concluded that with the heavier elements
as well as the fcc monocarbide phases -TC1x . All carbides
of group 4 and 5, the stoichiometric composition can more
of the composition T2 C have high- and low-temperature
easily be attained than with the carbides of the metals of the
modifications that differ only by the arrangement of the carbon
first long period. Indeed, vanadium carbide shows a maximum
atoms5 on the interstitial positions. Furthermore, a large variety
carbon content of VC0.92 . The thermochemical stability of the
of ordered hemicarbides T2 C have been identified by electron
carbides decreases with increasing group number. While the
microscopy and/or diffraction7,11 but have not been included in
monocarbides of groups 4 and 5 can be melted congruently,
the phase diagrams because of their dubious phase character.
the carbides of group 6 metals decompose peritectically Possibly these structures are affected by impurities.
before their melting points are reached. The monocarbide In these systems, the -phases -V4 C3x , -Nb4 C3x and
MoC decomposes in a peritectoid reaction at 1170 C into -Ta4 C3x are observed. These phases have a close-packed
Mo2 C + C. metal atom stacking sequence of 12 layers per unit cell
(ABABCACABCBC. . .) and a random occupancy of carbon
atoms in the octahedral interstices. Their actual compositions
5.2 Phase Equilibria deviate from the ideal crystallochemical C/T ratio of 3/4 (see
Section 2), a deviation that is largest for -V4 C3x where the
5.2.1 Group 4 Transition Metal Carbon Systems carbon content is below 40 at%. The stabilities and the homo-
geneity ranges of these phases were investigated by diffusion
Figure 2 shows the group 4 transition metal carbon couples.22 Peritectoid decomposition/formation of these -
systems,25 which are very similar to each other concerning T4 C3x phases occur in which also the -T2 C and -TC1x
the carbide phases: the monocarbides -TiC1x , -ZrC1x and phases are involved. Several ordered compounds have been
-HfC1x show extensive homogeneity ranges and have high observed in group 5 carbides8 even at high carbon contents
congruent melting temperatures. These phases are of the NaCl such as V6 C5 , V8 C7 and Nb6 C5 . The effect of ordering on the
type and are closely related in structure as well as in properties hardness has been investigated for -VC1x (see Section 8.5).
with the transition metal nitrides.
Carbon does not stabilize the hcp low-temperature 5.2.3 Group 6 Transition Metal Carbon Systems
modifications of these metals (in contrast to nitrogen) and the
solubility of C in the -phases is much smaller as compared The crystal structures of the phases in these systems are
to the group 4 transition metal nitride systems. characterized by the destabilization of the T6 C octahedral
4000 4300
3000 L
L 3500 L 3900
2500 3000 3500
2500 3100
T/C
T/C
T/C
2000
dTiC1X 2000 2700
1500 bTi(C)
dZrC1X
dHfC1X
1500 bZr(C) 2300
1000 b
aTi(C) 1000 1900 a
aZr(C)
500 500 1500
0 10 20 30 40 50 60 0 10 20 30 40 50 60 0 10 20 30 40 50 60
(a) At% C (b) At% C (c) At% C
Figure 2 Phase diagrams of the group 4 transition metal carbon systems. (a) titanium-carbon; (b) zirconium-carbon; (c) hafnium-carbon.
(Ref. 25. Reproduced by permission of Materials Information Society/ASM International)
CARBIDES: TRANSITION METAL SOLID-STATE CHEMISTRY 5
2000 2000
L 2200
1800
dVC1X
L
2000
b V2C 1800
T/C
T/K
1600
a V(C) 1800
1400
T/C
z V4C3x
Cr7C3
1600 1600
1200 (Cr)
0 10 20 30 40 50
Cr3C2
(a) V At% C 1400
Cr23C6
dNbC1X
2000
2200 1200
0 10 20 30 40 50
a Nb(C) b Nb2C
1800
T/C
T/K
(a) Cr At% C
2000
1600 3000
1800 hMo3C2
z Nb4C3x
L
1400 2500
0 10 20 30 40 50 dMoC1X
b
(b) Nb At% C
2000
2300 Mo(C)
T/C
d TaC1X
2500 1500
2200
a Ta(C) b Ta2C
2400
2100
1000
T/C
2300
T/K
2000
Mo2C MoC
1900 2200
500
z Ta4C3x 2100
1800
1700 2000 0
0 10 20 30 40 50 0 10 20 30 40 50 60
(c) Ta At% C (b) At% C
3000
Figure 3 Section of phase diagrams22 of the group 5 transition L g WC1X
WC
T/C
T/C
metal atom host lattice with interstitial carbon atoms. Cr3 C2 1000 gMn(c)
has trigonal prismatic structural elements in an orthorhombic
b Mn3C
lattice. A further orthorhombic chromium carbide phase with
Mn5C2
the composition Cr3 C is metastable and isotypic to cementite, 600
Mn(C)
Fe3 C. The phase Cr7 C3 has an orthorhombic arrangement of
Mn23C6
Mn7C3
metal atoms and is structurally closely related to the hexagonal
T2 C phases. While the hexagonal T2 C do not contain other
200
structural elements than T2 C octahedra, slightly distorted 0 10 20 30 40
T6 C trigonal prismatic structure groups can be observed in (a) At% C
Cr7 C3 . In ternary systems with hexagonal T2 X phases in the
boundary system, the solid solubility of Cr7C3 in the hexagonal 1600
dFe(C)
phases is considerable. In Cr23 C6 , each carbon atom has 8
L
metal neighbors in the form of a quadratic antiprism. In that 1400
respect the structure differs basically from all other transition
metal carbides. 1200
gFe(C)
T/C
The H-phases are a large family of ternary interstitial Table 2 Bulk properties of the H-phase related compound Ti3 SiC2 27
compounds. They have the general formula T2 MX, where T is
a transition metal, M is a group 2 or 6 element and X is C or N. Physical and electrical properties
Density (g cm3 ) 4.5
The structure can be described as alternating hexagonal layers
Electrical Conductivity at RT 106 (1 m1 ) 4.5
of octahedra consisting of carbon and main group element CTE 106 ( C1 ) 9
atoms (Figure 6). The structure of the H-phases is related to Thermal Properties
the structures of -Mo3 C2 , -NbN and -TaN (see Nitrides: Thermal Conductivity at RT (W m1 K1 ) 37
Transition Metal Solid-state Chemistry). Thermal Conductivity at 1200 C (W m1 K1 ) 32
The -phases have the general formula T14 T22 Cx or Service Temperature, Air ( C) 1200
Service Temperature, Inert, or ( C) 2000
T13 T23 Cx , where T1 and T2 are transition metals. There are
Vacuum
carbides, nitrides, and oxides with the -carbide structure. Mechanical Properties
Ward10 has summarized the structure of these phases, Elastic Modulus (GPa) 300
which are characterized by T6 C octahedra connected by Hardness Vickers (GPa) 4
common faces. Tensile Strength at RT (MPa)(brittle) 200
Tensile Strength at 1200 C (MPa)(ductile) 40
A further group of ternary carbides, T3 MC2 , where T
Flexure Strength at RT (MPa)(brittle) 400
is a transition metal and M is a main group element such Flexure Strength at 1200 C (MPa)(ductile) 100
as Si or Ge, features a close-packed stacking sequence of Compressive Strength at RT (MPa)(brittle) 1100
Si/Ge and T layers with the sequence (hhhc)2 and where the Compressive Strength at 1200 C (MPa)(ductile)
500
second h layer in this sequence is the Si/Ge layer. Barsoum Fracture Toughness KIC (MPa m) 8
Thermal ShockTc (100 m grain C 1400
et al.27 conducted an intensive investigation of the phase size)
Ti3 SiC2 in the past years. These phases (also nitride and Thermal ShockTc (5 m grain
C 700
carbonitride phases belong to this family) show an unusual size)
set of properties (Table 2) owing to the layered structure of
the unit cell. They are relatively soft but elastically stiff. Of
highest importance is the fact that these compounds can be aspects in complex carbides has been given by Nowotny and
easily machined by regular tools despite their good high- Benesovsky.28
temperature mechanical properties. They represent a new
class of solids that can be identified as thermodynamically
stable nanolaminates. A comprehensive treatment of structural
been claimed to be of consequence for the sintering behavior deficiency increases the low-temperature thermal conductiv-
and performance of carbonitride hardmetals (see Section 9.1). ity of -TiC1x but decreases the high-temperature thermal
conductivity.
Transition metal carbides have generally a significantly
lower thermal conductivity than isotypic transition metal
8 PROPERTIES OF TRANSITION METAL nitrides. Some values are given in Table 1 and a comparison
CARBIDES between these two groups is given in the article on (see
Nitrides: Transition Metal Solid-state Chemistry) as a
function of temperature.
8.1 Melting Points The thermal conductivity of WC33 is much higher than
that of the fcc transition metal carbides. The lower thermal
The transition metal carbides are some of the highest conductivity of fcc carbides has been attributed to their
melting known materials. -TaC0.89 melts congruently at generally nonstoichiometric composition and hence the higher
3985 C and -HfC0.94 congruently at 3950 C. The melting concentration of phonon scattering defects in the lattices, but
temperatures can be read from the phase diagrams presented can probably be explained by the stronger covalent bonding
in Section 5.2. in WC and hence the higher efficiency of the heat transport
by phonons.
8.2 Thermal and Electrical Properties The parallelism in properties between fcc transition metal
carbides and nitrides is also valid for room-temperature
The thermal conductivities of transition metal carbides electrical resistivity, which decreases with increasing carbon
increase with increasing temperature, an unexpected phe- content and increases with increasing temperature. Generally
nomenon that has been investigated extensively on titanium, the transition metal carbides have higher electrical resistivities
zirconium, hafnium and carbides and carbonitrides.31,32 Previ- than the transition metal nitrides. Figure 7 gives the electrical
ous studies have reported a linear increase of the thermal resistivities of Groups 4 and 5 transition metal carbides as a
conductivity with temperature, but more recent investi- function of carbon content, as compiled by Storms,2 compare
gations have revealed a nonlinear relationship.32 Carbon also Ref. 32. For the electrical resistivity of -HfC, values
220 220
Electrical resisivity [ cm]
180 180
140 140
100 100
60 60
20 20
0.5 0.6 0.7 0.8 0.9 1.0 0.5 0.6 0.7 0.8 0.9 1.0
(a) [C]/[Ti] [C]/[Zr]
80 80 80
40 40 40
0 0 0
0.7 0.8 0.9 1.0 0.7 0.8 0.9 1.0 0.7 0.8 0.9 1.0
(b) [C]/[V] [C]/[Nb] [C]/[Ta]
Figure 7 Electrical resistivity versus [C]/[T] ratio for -TiC1x , -ZrC1x (a), and fcc group 5 transition metal carbides (b), from Storms.
(Reprinted from Ref. 2. 1972, with permission from Elsevier)
CARBIDES: TRANSITION METAL SOLID-STATE CHEMISTRY 9
D0 E a
Compound (cm2 s1 ) (eV) (cm3 mol1 ) 300
8.5 Microhardness and Elastic Properties For Ti, Zr, and Hf carbonitrides, including also binary
carbides and nitrides, the Youngs, shear, and bulk modulus as
The Youngs moduli E of group 4 transition metal carbides well as the Poisson number have been measured by ultrasonic
are on the order of about several hundred GPa (Table 1) and measurements as a function of the C/N ratio.41 The data are
appear to depend on the carbon/metal ratio. This is at least given in Figure 10.
true for -TiC1x , where E increases with increasing [C]/[Ti] Many of the transition metal carbides such as TiC
approximately linearly from 200 GPa at TiC0.50 to 460 GPa are very hard compounds. In -TiC1x the microhardness
at TiC0.98 (Figure 9). Values for -ZrC1x and -HfC1x are increases with increasing carbon content, a phenomenon
370 480 and 420 460 GPa, respectively, for unspecified but that is probably closely related to the VEC, with the
probably near-stoichiometric compositions.39,40 The highest maximum stability at VEC = 8 at the composition TiC.
Youngs modulus is that of WC (Table 1) and has been Figure 11 shows this behavior for -TiC1x ,42 other
measured for temperatures of up to 2200 K.33 It drops almost data are contained in Table 1. Both microhardness and
linearly from about 710 GPa at room temperature to 557 GPa nanohardness were recently measured for Ti, Zr, and Hf
at 2200 K. carbonitrides as a function of the C/N ratio.41 The data are
VEC VEC
9.0 8.8 8.6 8.4 8.2 8.0 8.1 7.9 7.7 7.5 7.3
490 460
E
450 420
Elastic constants E, B, G (GPa)
E
410 380
370 340
330 300
290 260
B B
250 220
210 G 180 G
170 140
130 100
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
(a) Composition [C]/([C] + [N]) (b) Composition [C]/([C] + [N])
VEC VEC
9.0 8.8 8.6 8.4 8.2 8.0 9.0 8.8 8.6 8.4 8.2 8.0
470 490
E
430 E 450
Elastic constants E, B, G (GPa)
390 410
350 370
310 330
270 290
B B
230 250
190 G 210 G
150 170
110 130
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
(c) Composition [C]/([C] + [N]) (d) Composition [C]/([C] + [N])
Figure 10 Youngs (E), shear (G), and bulk modulus (B) of (a) Ti(Cx N1x ), (b) Ti(Cx N1x )0.81 , (c) Zr(Cx N1x ) and (d) Hf(Cx
N1x ), as a function of the C/N ratio as well as of the VEC. (Reprinted from Ref. 41. 2000, with permission from Elsevier)
CARBIDES: TRANSITION METAL SOLID-STATE CHEMISTRY 11
VEC VEC
9.0 8.8 8.6 8.4 8.2 8.0 8.1 7.9 7.7 7.5 7.3
34 34
30 Nanohardness 30
Hardness (GPa)
26 26 Nanohardness
22 22
Microhardness
Microhardness
18 18
14 14
10 10
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
(a) (b)
9.0 8.8 8.6 8.4 8.2 8.0 9.0 8.8 8.6 8.4 8.2 8.0
34 34
30 30 Nanohardness
Hardness (GPa)
Nanohardness
26 26
22 22
Microhardness
18 18
Microhardness
14 14
10 10
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
(c) Composition [C]/([C] + [N]) (d) Composition [C]/([C] + [N])
Figure 12 Nanohardness () and microhardness () for (a) Ti(Cx N1x ), (b) Ti(Cx N1x )0.81 , (c) Zr(Cx N1x ) and (d) Hf(Cx
N1x ) as a function of the [C]/([C] + [N]) ratio as well as of the VEC. For stoichiometric carbonitrides the two functions are practically
parallel, from Yang et al. (Reprinted from Ref. 41. 2000, with permission from Elsevier)
12 CARBIDES: TRANSITION METAL SOLID-STATE CHEMISTRY
40 9 USES
Vickers hardness [GPa]
30
9.1 Cemented Carbides (Hardmetals)
20
9.1.1 Metallurgy of Hardmetals and Cermets
10 Nanohardness
The most widely used transition metal carbide is tungsten
Microhardness carbide, hexagonal WC, which is employed as the hard
0
0 0.2 0.4 0.6 0.8 1 constituent in WCCo hardmetals. These hardmetals are
[N]/([C] + [N]) resp. [Ti]/([Ti] + [Ta]) sintered composite materials with 80 90% of hard particles
such as WC embedded in a ductile binder phase such as Co
40 and/or Ni. For these applications, WC combines a number of
Vickers hardness [GPa]
Table 4 Properties of some important Transition Metal Carbides, Nitrides, and Quarternary Carbonitrides
90 90
80 80
70 70
60 60
C
At%
%
50 WC
At
C
40 40 4 m 20 KV 17 851 S
W2C
30 30
Figure 16 Microstructure of a titanium carbonitride hardmetal
20 M6C 20
L (cermet) showing the core-and-rim type structure of hard particles
10 10
M12C
yet fully understood,50 because of the complexity of the
Co 10 20 30 40 50 60 70 80 90 W multicomponent system. The theoretical background of the
b m
phase reactions within the system TiMoCN was developed
At% W
by Rudy,30 who claimed that the quaternary compound
(Ti,Mo)(C,N) with a random distribution of the metals Ti
Figure 14 Phase diagram of the WCCo system at 1350 C and Mo on the metal sites and the nonmetals C and N on
the nonmetal sites should undergo a decomposition with the
formation of two isotypic fcc phases but with a preferential
arrangement of N around the Ti atoms and Mo around the
C atoms. This decomposition is of a spinodal type, which
is a decomposition induced by local composition fluctuations
without any activation energy rather than a classical nucleation
and growth process. The question whether the spinodal
decomposition is a necessary prerequisite for the core-and-
rim formation of the hard component is still the topic of
discussions because core-and-rim structures may develop via
reactions of the hard constituents with the liquid binder metals
as well.
The core-and-rim type structure has been claimed to
have a favorable influence on the mechanical properties
because the molybdenum-containing rim is much better
Figure 15 Microstructure of a coarse WCCo hardmetal with gray wetted by the binder alloy than the nitrogen-containing
WC particles embedded in a Co matrix, the size of the largest grains core. Modern Ti(C,N) hardmetals have been successfully
is about 20 m
applied for finishing operations of high-strength steel grades
and ductile cast irons at high cutting speeds but with
introduced as a further constituent. Generally, these titanium moderate cross section of the chips. The main advantages of
carbonitride hardmetals, often called cermets (an artificial Ti(C,N) hardmetals over conventional hardmetals are the high
word coined from the words ceramic and metal because of chemical resistance and the low frictional welding tendency,
the combination of a brittle ceramic component, which, resulting in longer life of the cutting edge and a good workpiece
however, has metallic transport properties as shown above, surface. For some applications, Ti(C,N) cermets do outperform
and a binder metal), are comparable with respect to properties even coated WC hardmetals.
and microstructure to WC-based hardmetals.
The compacted powder mixtures of these materials are 9.1.2 Cemented Carbide Grades
usually liquid phase sintered with Ni or NiCo binder metal
alloys. The microstructure features a core-and-rim structure The cemented carbides are used for a variety of different
of the hard phase with a molybdenum- and carbon-rich applications ranging from metal cutting, drilling, and milling
(Ti,Mo)C rim and a titanium- and nitrogen-rich Ti(C,N) (steel and nonferrous alloys) over wood cutting to drilling
core. This microstructure can be made visible in the SEM of circuit boards for electronic devices as well as for
(Figure 16). The metallurgy of the phase reactions is not structural parts such as dies and cutters for the paper
14 CARBIDES: TRANSITION METAL SOLID-STATE CHEMISTRY
all tool tips for metal cutting are coated. Modern multilayer
coating feature a combination of different layers, where TiN
is often the base layer adjacent to the substrate, Ti(C,N) is an
intermediate layer and TiN is the top layer. This should provide
a smooth variation of properties across the layer, from good
adherence to the hardmetal to the high chemical inertness and
low tool-workpiece frictional welding tendency of TiN. Such
Figure 17 Examples of different cutting inserts used in cutting layers are usually made by CVD processes where a volatile
industry (Kennametal-Widia GmbH) component such as titanium tetrachloride is reacted with a
10 REFERENCES
Figure 19 Microstructure of a functionally graded hardmetal 3. L. E. Toth, Transition Metal Carbides and Nitrides, Academic
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4. H. J. Goldschmidt, Interstitial Alloys, Butterworths, London,
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are multilayer coatings that consist of carbonitrides, carbides, A. Finel, in The Physics and Chemistry of Carbides, Nitrides
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ternary and quaternary carbonitrides51 such as Zr(C,N) and Dordrecht, 1990, p. 329.
(Ti,Hf )(C,N) as well as mixed oxides such as Al2 O3 /TiO2 , 9. P. Villars and L. D. Calvert eds, Pearsons Handbook of
Al2 O3 /TiO2 /HfO2 . Crystallographic Data for Intermetallic Phases, 2nd edn., ASM,
PVD (physical vapor deposition) methods can be applied Metals Park, OH.
whenever the substrate temperature has to be kept lower than 10. R. Ward, in MTP International Review of Science, Inorganic
600 C (e.g. for quenched-hardened steel items); they make Chemistry Series One, ed. D. W. A. Sharp, Butterworths,
use of a variety of techniques ranging from sputtering to ion London, 1972, Vol. 5.
beam deposition.
11. T. Epicier, in The Physics and Chemistry of Carbides, Nitrides
Another recent development on the field of wear-resistant
and Borides, ed. R. Freer, Kluwer Academic Publishers,
layers is the formation of graded zones in functionally graded
Dordrecht, 1990, p. 297.
hardmetals FGHMs (cemented carbides).52 These near-surface
zones are formed by diffusion of mainly nitrogen into a 12. W. Lengauer, in Handbook of Ceramic Hard Materials, ed.
Ti-containing hardmetal so as to create a Ti(C,N)-enriched R. Riedel, Wiley-VCH, Weinheim, 2000, Vol. I, p. 202.
surface. Some of these FGHMs show a smooth increase of 13. A. Neckel, in The Physics and Chemistry of Carbides, Nitrides
the nitride phases towards the surface and thus a absence of and Borides, ed. R. Freer, Kluwer Academic Publishers,
a macroscopic interface. An example of an microstructure is Dordrecht, 1990, p. 458.
given in Figure 19. The lifetime of such graded hardmetals is 14. P. Blaha and K. Schwarz, Int. J. Quantum Chem., 1983, 23,
more than tenfold of that of untreated grades. Such FGHMs 1535.
can be used as a substrate for nitride and carbonitride as 15. P. McKenna, US Patent 3 379 503 1968; Chem. Abstr., 1968,
well as diamond coatings and outperform hardmetals without 68, 116 088.
graded substrate.
16. J. Billingham, P. S. Bell, and M. H. Lewis, J. Cryst. Growth,
1972, 13/14, 693.
9.3 Diffusion Barriers 17. P. McKenna, Met. Prog., 1939, 36, 152.
18. G. F. Bastin and H. J. M. Heijligers, J. Microsc. Spectrosc.
Transition metal carbides can be used as diffusion barriers Electron., 1986, 11, 215.
like transition metal nitrides in multilayer metallization
19. W. Lengauer, D. Rafaja, R. Taubler, C. Kral, and P. Ettmayer,
schemes for integrated circuits.53 Layers on the order of
Acta Metall. Mater., 1993, 41(12), 3505.
100 nm are applied and are produced by sputtering methods.
The high chemical stability of these transition metal carbides, 20. W. Lengauer, D. Rafaja, G. Zehetner, and P. Ettmayer, Acta
especially those of group 4, are exploited to prevent interaction Mater., 1996, 44(8), 3331.
of metal or component layers such as silicon, aluminum, and 21. W. Lengauer, J. Bauer, M. Bohn, H. Wiesenberger, and
silicides upon thermal load in production processes. This load P. Ettmayer, Mikrochim. Acta, 1997, 126, 279.
would cause electrical or even structural deterioration of the 22. H. Wiesenberger, W. Lengauer, and P. Ettmayer, Acta Mater.,
multilayer packages. 1998, 46(2), 651.
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23. W. Mayr, W. Lengauer, D. Rafaja, J. Bauer, and M. Bohn, J. 38. F. J. J. van Loo and G. F. Bastin, Metallurg. Trans. A, 1989,
Phase Equilib., 1999, 20, 35. 20, 403.
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P. S. Rudman, J. Stringer, and R. I. Jaffee, McGraw-Hill, New- Films, 1987, 153, 37.
York, 1967, p. 419. 40. C. Kral, W. Lengauer, D. Rafaja, and P. Ettmayer, J. Alloys
25. T. B. Massalski ed. Binary Alloys Phase Diagrams, 2nd edn., Compd., 1998, 265(1 2), 215.
ASM International, Metals Park, OH, 1991.
41. Q. Yang, W. Lengauer, T. Koch, M. Scheerer, and I. Smid, J.
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Monatsh. Chem., 1968, 99, 1020.
42. J.-L. Chermant, Delavignette, A. Deschanvres, J. Less-Common
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43. V. N. Lipatnikov, W. Lengauer, P. Ettmayer, E. Keil,
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Nitrides and Borides, ed. R. Freer, Kluwer Academic
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Carbon: Fullerenes 1.1 History
Figure 1 Structures of the three main forms of carbon: (a) diamond; (b) -graphite; and (c) buckminsterfullerene (Ih -C60 ), the archetype of
the fullerene family
Data
Transiac 2001 of data
1000 of 1000 shots
7000
6000
5000
4000
3000
2000
1000
0
15 20 25 30 35 40 45 50 55 60 65
941985 Time (microseconds) 18:56:4.7 Figure 3 Photograph (by transmitted light) of the fullerene crystals
formed by gentle evaporation of the red/brown benzene extract from
soot produced by the arc vaporization of graphite. (Reprinted with
Figure 2 Time-of-flight mass spectrum of carbon clusters produced permission of Macmillan from W. Kratschmer et al.4 )
by laser vaporization of graphite (September 4, 1985) under
conditions which first exhibited the dominance of the C60 cluster and
led to the recognition that 60 might be a magic number. (Reprinted one. In general the simpler fullerenes are referred to by
with permission from Ref. 2a. 1991 American Chemical Society) their symmetry and size, e.g. Ih -fullerene-60, although for
convenience and brevity the fullerene cage structure is often
assumed and the molecular formula used, e.g. Ih -C60 , D2 -C76 ,
or simply by the molecular formula alone if only one cage
values of n (n = 1; C22 cannot be constructed with only
symmetry is known, e.g. C60 , C70 .
hexagonal and pentagonal rings). Fullerenes therefore contain
an even number of carbon atoms arranged as a combination of
V E+F =2 (1)
12 pentagonal rings and any number n (n = 1) of hexagonal
rings, e.g. the archetypal fullerene, buckminsterfullerene (Ih - 3n3 + 2n4 + n5 n7 2n8 3n9 = 12 (2)
C60 ), consists of 12 (isolated) pentagons and 20 hexagons
(Figure 1(c)). Buckminsterfullerene is the only fullerene to Heterofullerenes are derivatives of fullerenes in which one
have acquired an accepted trivial name, albeit a slightly long or more carbon atoms have been replaced by a different
CARBON: FULLERENES 3
element without disruption of the basic cage structure, e.g. isomer of C60 for which all the pentagonal rings are
C59 B. indeed isolated from one another. Using this principle the
Endohedral fullerenes are molecules in which an atom or fullerene D5h -C50 is (correctly) predicted to display enhanced
group of atoms is encapsulated within the cage. In the case stability since it is the smallest system to exclude triplets of
of metal encapsulation the compounds are commonly referred edge-sharing pentagons, although stability is also dependent
to as endohedral metallofullerenes. The accepted symbol to on several other factors, including electronic structure and
indicate encapsulation is @, e.g. U@C28 , La@C82 . molecular strain (Section 2.3). The lowest energy structures
of all the smaller fullerenes (Cn , 20 n 70) have been
calculated, and this study confirms that those isomers with the
2.2 Fullerene Structure fewest edge-sharing pentagons are indeed the most stable.10
Under the appropriate experimental conditions (single photon
As the general formula for a fullerene is C20+2n (n = 1), ionization), the enhanced stability of the smaller fullerene
the three simplest fullerenes are Ih -C20 , D6d -C24 , and D3h -C26 cations C28 + , C32 + , and C50 + is apparent (Figure 5).11
(Figure 4), and there is only one isomer for each of these. To date, all isolable nonderivatized fullerenes satisfy the
For the larger fullerenes more structures are possible, the IPR, although this rule does not necessarily predict that a
number of which increases rapidly with cage size and can be fullerene will be stable or isolable (Section 2.3). After Ih -
calculated using the Ring Spiral Algorithm.6 For fullerenes up C60 the next possible IPR fullerene structure is D5h -C70 , and
to C380 this algorithm generates all isomers and reduces each historically the observation that C60 and C70 displayed special
to a unique sequence of numbers and therefore provides an stability provided strong evidence for both the cage structures
unambiguous (although incomprehensible) naming scheme.7 of these molecules and the IPR.2 Other fullerenes which have
The ring spiral algorithm shows that the C60 molecule
been characterized to date are D2 -C76 , C2v -C78 , C2v -C78 ,
has 1812 different possible isomeric structures; however, D3 -C78 , C2 -C82 (maybe more than one isomer), C2v -C82 , C3v -
experimentally only the Ih -C60 isomer is observed. The C82 , D2 -C84 , and D2d -C84 (Section 5.3).1215 D2 -C76 has the
observation that unsaturated organic molecules containing interesting feature of being the smallest, chiral fullerene so far
edge-sharing pentagons tend to be unstable is the basis of isolated (Figure 6). For C78 and the larger fullerenes there are
the Isolated Pentagonal Rule (IPR) for fullerene stability.2,8,9 many possible IPR isomers, although only a few have been
This rule is elegantly confirmed by Ih -C60 being the only isolated to date. Mixtures containing fullerenes larger than
Figure 4 Possible cage structures and idealized symmetries of some of the smaller fullerenes
4 CARBON: FULLERENES
C60+ 57 58
43 44 45 46
24 25 26 27
23 9 28
42 8 47
10
22 7 11 29
21 6 12 30
C50+ 41 1 48
+
5 2
C28 20 13
40 4 3 31
19 14
C32+ 55 39 32 49
C24+ 56 38 18 17 16 15 33 59
37 34
54 50
20 40 60 80 100 53 36 35 51
Carbon atoms per cluster
52
Figure 6 The spectroscopically confirmed cage structures of the first three fullerenes to be isolated in macroscopic amounts; Ih -C60 , D5h -C70 ,
and the chiral fullerene D2 -C76
CARBON: FULLERENES 5
C540
(a)
C540 (b)
t1g 0.382 b
Ih-C80
t1u 0.139 b
hu 0.618 b
3.3 Toxicity
Since the synthesis of macroscopic amounts of C60 was
achieved in late 1990, several strategies for each stage of The short and long term toxicities of the fullerenes and
fullerene synthesis and purification have been developed. related materials are unknown, and they should therefore be
8 CARBON: FULLERENES
handled with all suitable precautions. The soot generated from an inert carrier gas.39 A broad distribution of products is seen,
graphite vaporization is very light and fluffy, and contains with distinct maxima corresponding to multiples of the starting
varying amounts of nanofiber structures. Such materials should fullerene: C118 + and C178 + for pure C60 , and C138 + for pure
not be inhaled because fine particulates are known to be C70 . Coalescence is not observed in the absence of the carrier
responsible for the crippling and ultimately fatal conditions gas, indicating that the hot vapor must be constrained in order
of asbestosis, silicosis, and emphysema. Although no studies for reaction to take place. Under these conditions, not only
on the toxicity of C60 have been reported, it is known to be do the initially formed C120 + and C180 + molecules fragment
a potent sensitizer for singlet oxygen and should therefore be by loss of multiples of C2 , but aggregation to C120+2n + and
handled with caution.37 C180+2n + also occurs.
Density47 1.65 g cm3 isotropically and has a very short rotational correlation time
Bulk modulus47 18 GPa ( 9 ps), faster even than in tetrachloroethane solution
Refractive index47 2.2 (630 nm)
( 15 ps). A phase transition from fcc (Fm3m) to a
Heat of combustion (crystalline C60 )37 545 kcal mol1
Electron affinity47 2.6 2.8 eV simple cubic structure (Pa3) occurs at 260 K. Neutron
First ionization energy47 7.6 eV diffraction and 13 C NMR studies of this phase reveal that
Band gap47 1.9 eV the C60 molecules appear to be jumping between symmetry-
Solubility (303 K)48 equivalent orientations. Below 90 K this motion is frozen,
CS2 5.16 g L1 yielding a partly disordered structure in which the main
Toluene 2.15 g L1 inter-C60 interaction is between a relatively electron rich
Benzene 1.44 g L1
six six ring fusion (double bond) of one molecule and an
CCl4 0.45 g L1
Hexane 0.04 g L1 electron deficient five-membered ring of an adjacent one
(Figure 14).50
10 CARBON: FULLERENES
13
5.3 C NMR Spectroscopy C60
For each of the first two isolable fullerenes (C60 and C70 ),
only one IPR isomer is possible; however, the next fullerene
(C76 ) has two possible IPR structures, but only one has been
observed. For C78 and higher fullerenes, several isomers are (b)
found to coexist. In the cases where sufficient material has d C70
b
been isolated, the composition of these isomer mixtures and
e
the molecular symmetries of their components have been a
c
investigated by 13 C NMR spectroscopy.
The study of the fullerenes by 13 C NMR spectroscopy is
not straightforward. 13 C has a low natural isotopic abundance
(1.11%) and a low relative receptivity. In addition, the carbon
(c)
atoms in fullerenes have relatively long relaxation times and
spectra for the higher, less symmetric fullerenes can only 150 140 130
ppm
be obtained within a reasonable time by using paramagnetic
relaxation reagents, typically Cr(acac)3 . a c b d e d b c a
The carbon atoms in C60 are equivalent, and as expected
only a single line is observed: 142.7 ppm (C6 D6 ). C70
has D5h symmetry and as there are five distinct carbon
atom environments, a five-line spectrum is observed: 150.1,
147.5, 146.8, 144.8, and 130.3 ppm (C6 D6 ) of intensity ratio
10:20:10:20:10 (Figure 15).5 The initial assignments based on
chemical intuition have been subsequently confirmed by 2D
13
C NMR.2 The upfield line (130.9 ppm) corresponds to the
10 graphitic atoms around the waist (type e), that lie at the
intersection of three six-membered rings.
A similar atom type partition is found for C76 .12 This
molecule has D2 symmetry and the expected 19-line spectrum
is observed. The four upfield lines ( < 137.1 ppm) are
assigned to the 16 (4 4 atoms) graphitic carbons, whereas
the remaining 60 carbons (15 4 atoms, > 141.3 ppm) Figure 15 13 C NMR spectra and assignments of C60 and C70 .
make up the 12 five-membered rings. Some other higher (Ref. 5. Reproduced by permission of The Royal Society of
fullerenes have been successfully characterized as mixtures of Chemistry)
isomers. Thus for C78 , five isomers are possible, but only three
have been characterized by 13 C NMR: C2v (21 lines), C2v (21
lines), and D3 (13 lines). For C82 , nine isomers are possible (Figure 16).54 Four similar IR bands are also observed in
and three (possibly with traces of a fourth) have been seen, at an emission spectrum from hot C60 vapor.2 Furthermore, all
least one C2 (41 lines), C2v (17 lines), and C3v (12 lines). For 10 allowed bands are seen in the Raman spectrum: 1573,
C84 , 24 isomers are possible, but only two have been seen, D2 1467, 1422, 1250, 1099, 772, 711, 495, 429, and 272 cm1 .
(21 lines) and D2d (10 lines).1315 Pure 13 C60 has also been prepared and the IR bands are
shifted by the predicted amount to 1375, 1138, 554, and
506 cm1 .55
5.4 Vibrational Spectroscopy
The IR (Figure 16) and Raman spectra of pure C70 ,2,54
For pure C60 all four allowed IR transitions are observed and the 1450 500 cm1 region of the solution IR spectrum
as characteristic, sharp bands: 1429, 1183, 577, and 528 cm1 (CS2 ) of C76 have also been reported.12 They are more
CARBON: FULLERENES 11
C60
Optical density
C60
1500 1400 1300 1200 1100 1000 900 800 700 600
cm1
C70
C70
Optical density
S S S S
S S S S
(4)
S S S S S S S
S
S S S S S S S S
(5)
Te Te
(h5-C5H5)2FeII
Te Te
(6) (7)
6.2.2 Halogenation
C60 reacts with liquid Br2 to yield C60 Br24 (Figure 23), in (8) (9)
which all 24 bromine atoms are equivalent.90 It is noteworthy
that 24 is the maximum number of groups that can be
arranged on C60 without resorting to the sterically unfavored
1,9-addition (Figure 22). The use of a cosolvent for the
bromination results in the formation of partly brominated
products: C60 Br8 from CS2 , and C60 Br6 from C6 H6 or O O
CCl4 (Figure 24).91 In both cases the bromine atoms are
gregarious, forming localized aggregates on the cage, rather
than being dispersed. In C60 Br8 the structure corresponds
to a portion of the C60 Br24 molecule, whereas C60 Br6 (10) (11)
contains one unfavorable eclipsing interaction. This latter
structure may arise by successive 1,7-additions to form the
stable cyclopentadienyl radical [C60 Br5 ], which is trapped Osmylation of C60 with OsO4 , in the presence of 4-t-butyl-
by addition of the central bromine atom (Br ). All the pyridine (L), yields the osmyl ester C60 [OsO4 L2 ] (12), the
brominated derivatives may be reconverted into C60 by heating first structurally characterized C60 derivative.67,95 The OsO4
to 100 150 C in vacuo. adds across a six six ring junction, in a similar manner to the
The trend to weaker C60 halogen bonds continues dioxolane derivative (9), and the two sp3 hybridized carbon
with I2 , and indeed no derivative of C60 with iodine atoms are moved away from the center of the cage: center-to-
atoms covalently bound to the cage has been reported to C(sp3 ) distances, 3.80 A; average center-to-C(sp2 ) distance,
CARBON: FULLERENES 17
3.55 A. The bis-osmyl ester C60 [OsO4 L2 ]2 has been prepared these derivatives appear to be mixtures of isomers of unknown
as a mixture of five isomers and probable structures for all structure; however, reaction of C60 with one equivalent of t-
five compounds have been deduced from 1 H and 13 C NMR BuLi or EtMgBr followed by quenching with water yields the
studies of the separated components.96 1,9-disubstituted products C60 RH (13) (R = t-Bu, Et) in up to
50% yield.99 The intermediate mono-substituted anion [C60 -t-
Bu] (14) has been isolated as the green microcrystalline salt
O [Li(THF)4 ][C60 -t-Bu],100 and is a very weak base (cf. [C60 H] ,
O L
Section 6.2.1). Protonation yields C60 (t-Bu)H (pKa 5.7, see
C60 OsVI
L Acids & Acidity) as either the 1,7- or 1,9-isomer (Figure 22),
O
O depending the source of H+ . The 1,7-isomer is a kinetic
product and slowly converts into the thermodynamically more
(12) stable 1,9-isomer.
C60 Me6 and C60 Me8 ,37 an interesting observation in the light R R R R
of the known stability of C60 Br6 and C60 Br8 (Section 6.2.2).
The mechanism for the formation of such highly alkylated
R R
derivatives is not known, but may indicate rapid electron
transfer from unreacted C60 6 to partially methylated C60 . All (15) (16)
18 CARBON: FULLERENES
C60 reacts with benzyl radicals to give addition used to prepare soluble bis-homofullerenes as models for the
products C60 (CH2 Ph)n (n 15), as determined by mass corresponding polymer systems.111 The electrochemical and
spectrometry.102 The formation of allyl (15) and cyclopen- spectroscopic properties of the bis- and polyhomofullerenes
tadienyl (16) radical sites on the cage has been revealed by are not significantly perturbed compared to the monomers.
ESR spectroscopy and these sites are thought to arise from
multiple 1,7-additions (cf. [C60 Br5 ], Section 6.2.2). The cor-
responding reaction of C60 with the p-xylylene diradical (17) Ar + N
gives an interesting polymeric material.103 N N Ar
C60 N C60
Ar Ar
Ar Ar
H2C CH2
(20) (21) (22)
(17)
The parent dihydrohomofullerene C60 (CH2 ) (23) is
prepared by reaction of C60 with CH2 N2 . In this case the
Under appropriate conditions the addition of a single radical
intermediate pyrazoline is isolable at room temperature, but
(R) to C60 is observed. In [C60 R] the radical is not delocalized
loses N2 upon heating (110 C).112 Interestingly 1 H and 13 C
over the cage but spin density is almost exclusively restricted
NMR studies show that the CH2 N2 molecule has added across
to the 2, 5, 7, 9, and 11 positions (see 14). Variable temperature
a six six ring fusion in the pyrazoline, whereas upon loss of
ESR studies of the bulky group derivatives (R = t-Bu, CCl3 ,
N2 the CH2 group migrates to a five six ring fusion. The two
CBr3 ) indicate that the radical is in equilibrium with its dimer,
previously equivalent protons are now in distinct chemical
which is believed to be linked through the 7 or 11 positions as
environments: 1 H NMR, 2.87 (Ha ) and 6.35 (Hb ) ppm, and
these are the most sterically accessible.104,105 For the addition
Jab = 9.7 Hz.
of a single radical to C70 , the formation of three of the five
possible different isomers has been established by ESR.106
The reaction of C60 with benzyne yields the adducts
C60 (C6 H4 )14 , of which the monoadduct has been isolated
and characterized by 1 H and 13 C NMR.107 The benzyne adds
across a six six ring fusion with the formation of a four-
H C H
membered ring. C60 also forms Diels Alder adducts with
dienes, although the products are difficult to characterize and
the reaction is often reversible.84 The diene (18), however,
cycloadds at a six six ring fusion of C60 , and subsequent loss
of CO ensures the irreversible formation of the stable product
(19), which has been structurally characterized.108 (23)
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Carbon: Inorganic tris(pentachlorophenyl)methyl, (C6 Cl5 )3 C, is particularly
stable.1
Chemistry 2. Exceptional examples of carbon atoms with apparent
coordination numbers greater than four include five-
coordinate carbon atoms in bridging alkyl groups in
Tomislav Friscic & Leonard R. MacGillivray metal alkyls (e.g. Al2 (CH3 )6 ), five- and six-coordinate
University of Iowa, Iowa City, IA, USA carbon atoms in deltahedral carboranes of the general
formula C2 Bn2 Hn (6 n 12), and five-, six-, and
Based in part on the article Carbon: Inorganic Chemistry by R. Bruce eight-coordinate carbon atoms in transition metal carbide
King which appeared in the Encyclopedia of Inorganic Chemistry, clusters such as a five-coordinate carbon in the center of
First Edition.
an Fe5 square pyramid in Fe5 (CO)15 C, a six-coordinate
carbon in the center of an Ru6 octahedron in Ru6 (CO)17 C,
1 Introduction 1 and an eight-coordinate carbon in the center of a Co8
2 Carbon Isotopes and Elemental Carbon 1 square antiprism in the anion Co8 C(CO)18 2 .
3 Carbon Halides 2 3. The high carbon carbon bond strength leads to the
4 Carbon Oxides 3 unusual stability of catenated carbon compounds: the
5 Carbon Oxyacids and Oxyanions 4 basis of organic chemistry. Thus the CC bond strength of
6 Carbon Sulfur Derivatives 5 356 kJ mol1 is comparable to the CO bond strength of
7 Cyanides and Related Compounds 6 336 kJ mol1 . This contrasts with the heavier congener
8 Carbon-based Molecular Ladders 9 of carbon, silicon, as well as with sulfur: SiO bonds
9 Related Articles 12 (368 kJ mol1 ) and SO bonds (330 kJ mol1 ) are
10 Further Reading 12 much stronger than SiSi bonds (226 kJ mol1 ) and SS
11 References 12 bonds (226 kJ mol1 ).
Carbon is the basis of organic chemistry; there are more 2.1 Isotopes of Carbon
compounds of carbon than of any other element except Table 1 summarizes some of the important properties of
hydrogen and possibly fluorine. However, most of the the carbon isotopes. Note that only the rare (1%), naturally
chemistry of carbon is the province of organic chemistry occurring, stable carbon isotope, namely, 13 C, has a nuclear
and thus not covered in this encyclopedia. The inorganic spin and is observable by NMR.2 The organic chemist is
chemistry of carbon discussed in this article, which is an fortunate that 99% of natural carbon is the isotope 12 C with
update of an excellent article written previously by professor no nuclear spin, so that proton and carbon-13 NMR spectra of
R. Bruce King (University of Georgia, Athens), includes organic compounds are not complicated by spin spin splitting
the allotropic forms of elemental carbon, simple molecular arising from adjacent carbon atoms. The radioisotope3 14 C is
carbon halides and oxides, carbon oxyacids and oxyanions, made by thermal neutron irradiation of lithium or aluminum
carbon sulfur derivatives, simple cyano derivatives, and nitride (equation 1). It decays back to stable 147 N by
carbon-based molecular ladders. emission, with a half-life of 5570 years (equation 2). Cosmic
Carbon chemistry has the following features: rays generate thermal neutrons, which leads to the formation
of 14 CO2 in the atmosphere (equation 1). Metabolism of
1. Carbon normally forms a total of four bonds including
both - and -bonds. The coordination number of a Table 1 Properties of the Carbon Isotopes
carbon atom forming four bonds can be two (C,
as in alkynes, or =C=, as in allene), three (=C<, as Natural
in alkenes), or four (as in alkanes) with linear, planar abundance NMR
triangular, and tetrahedral geometries, respectively. The Isotope (%) Half-life Spin sensitivitya
+
carbon atoms in carbon monoxide ( CO ) and the 12
C 98.89 Stable 0 0
+ 13
C 1.11 Stable 1/2 0.0159
isocyanide carbon atom in isocyanides ( CNR ) have
14
C 1.2 1010 5570 years, 0 0
coordination numbers of only one. Stable trivalent carbon
a
free radicals, R3 C, can be isolated if R is an aryl group; Relative to the proton for equal numbers of nuclei.
2 CARBON: INORGANIC CHEMISTRY
this 14 CO2 by living organisms is the basis of radiocarbon to electrical conductivity. The average CC bond order in
dating. graphite is 1.33, corresponding to a C C distance of 1.415 A.
By contrast, the average CC bond order in benzene is 1.5,
14
7N + 10 n 14
6C + 11 H (1) corresponding to the expected shorter C C distance of 1.39 A.
14 14
+ The most stable and common form of graphite is hexagonal -
6C 7N (2)
graphite with an ABABAB. . . stacking of the graphite layers.
However, rhombohedral -graphite with an ABCABC. . .
2.2 Allotropes of Carbon stacking of the layers is also known. Strong oriented graphite
fibers can be obtained by pyrolysis of fibers of organic
Carbon forms three types of allotropes: diamond, graphite, polymers such as poly(acrylonitrile). Amorphous carbons
and the recently discovered fullerenes. The properties of these (carbon black, soot, charcoal, etc.) are microcrystalline forms
allotropes are compared in Table 2. of graphite; their physical properties depend upon their surface
area and the nature of their surface (e.g. the presence and type
of oxygenated groups).
2.2.1 Diamond4 Molecules and ions can penetrate between the layers of
Diamonds are found naturally in Kimberly, South Africa, graphite to form interstitial or lamellar compounds. These
in ancient volcanic pipes embedded in a relatively soft, so-called intercalation compounds are of two types, namely,
dark colored basic rock in low concentrations (1 part nonconducting compounds, in which the planarity of the
per 1.5 107 ). The structure of diamond consists of an graphite layers is destroyed, and conducting compounds, in
infinite three-dimensional lattice of sp3 carbon atoms in which the planarity of the graphite layers is preserved (see
which there are interlocking six-membered C6 rings, similar Intercalation Chemistry).7,8
to those in cyclohexane or adamantane, and CC distances of
1.514 A. Diamond is normally found in the cubic form, but
a hexagonal form (lonsdaleite) is found in certain meteorites 2.2.3 Fullerenes9,10
and is available synthetically. Diamond is the hardest solid Fullerenes are large molecular carbon cages that are
known and has the highest melting point (4000 C) and isolated by extraction of specially prepared soot with organic
thermal conductivity, as well as the lowest molar entropy solvents such as benzene. A rich source of fullerene is
(2.4 J mol1 K1 ) of any element. Diamond is an insulator. The soot made by arcing graphite rods in a helium atmosphere
density of diamond (3.51 g cm3 ) is much greater than that of at 200 Torr pressure.11 The most common fullerene is C60 ,
graphite (2.22 g cm3 ) so that high pressures (e.g. >125 kbar) which has a truncated icosahedral soccer ball structure with
can be used to convert graphite to diamond even though icosahedral (Ih ) symmetry. Less symmetrical fullerenes with
graphite is thermodynamically more stable than diamond by larger numbers of carbon atoms are known. C70 is the next
2.9 kJ mol1 . In order to attain useful rates for the high- most abundant after C60 ; C76 and C84 are also known (see
pressure conversion of graphite to diamond, a transition metal Carbon: Fullerenes).
catalyst such as Cr, Fe, or Pt is used. Diamond burns in air at
elevated temperatures (600 800 C).
Graphite consists of planar layers of hexagons of sp2 Carbon tetrafluoride, CF4 , mp 185 C, bp 128 C, which
hybridized carbon atoms with a separation of 3.35 A between is the end product of the fluorination of carbon compounds,
layers. The relatively slight forces between graphite layers is a very stable gas. It can also be made by the fluorination
are consistent with its softness and lubricity. The infinite of silicon carbide (equation 3). The SiF4 is removed from
delocalization of -electrons in the graphite structure leads the CF4 by passing the product gases through 20% aqueous
NaOH, which removes the SiF4 as soluble sodium silicate but
Table 2 Properties of the carbon allotropes leaves the CF4 unaffected. This major difference in hydrolytic
reactivity of CF4 and SiF4 is a consequence of accessible d
Allotrope C Hybridization Structure orbitals on silicon but not on carbon.
Diamond sp3 Infinite 3D-lattice
Graphite sp2 Infinite 2D-planar layers SiC + 4F2 SiF4 + CF4 (3)
of hexagons
Fullerenes sp2 Finite Cn cages with 12 Organic compounds containing only carbon and fluorine
pentagons and n 12
hexagons are called fluorocarbons; the chemistry of fluorocarbons is
a vast area far beyond the scope of this encyclopedia.1215
CARBON: INORGANIC CHEMISTRY 3
General routes to saturated fluorocarbons include the Carbonyl halides, O=CX2 (X = F, Cl, Br, I), are all
fluorination of hydrocarbons with higher valent fluorides known, although the existence of COI2 has recently been
such as CoF3 or the fluorination of chlorocarbons with questioned.18 The fluoride and chloride are made by reaction
SbF3 , often in the presence of catalytic amounts of SbV . of carbon monoxide with the corresponding halogen; the
Since such fluorination procedures usually add fluorine bromide is made by the partial hydrolysis of CBr4 with
to all carbon carbon double and triple bonds giving concentrated sulfuric acid. Carbonyl chloride, O=CCl2 , bp
products with exclusively carbon carbon single bonds, +7.6 C, also known as phosgene (from = phos for
unsaturated fluorocarbons normally require indirect methods light and - = -genes for form, relating to its formation
of synthesis, generally using dehalogenation reactions by from CO + Cl2 in sunlight), is a toxic gas smelling like new-
metals such as zinc or dehydrohalogenation reactions with mown hay, which was used as a war gas in World War
bases. Fluorocarbons have diverse chemical and physiological I. Thiocarbonyl chloride or thiophosgene, S=CCl2 , is an
properties. Thus poly(tetrafluoroethylene), (CF2 CF2 )n , evil-smelling orange toxic liquid, bp 73 C.19
commonly known as Teflon, is very chemically inert
and has a low coefficient of friction. Octafluoroisobutene,
(CF3 )2 C=CF2 , is highly toxic, but other fluorocarbons,
such as perfluorodecahydronaphthalene, C10 F18 , are so 4 CARBON OXIDES
physiologically inactive that they are the active components
of blood substitute, because of the relatively high solubility of
The oxides of carbon include the very stable and abundant
oxygen in fluorocarbons.16
CO and CO2 , the unstable but isolable C3 O2 , and more
Carbon tetrachloride, a liquid with mp 23 C and bp
complicated carbon oxides derived from organic backbones
76 C, is a common solvent and is useful for converting
by removal of all hydrogen, for example, C12 O9 , from the
metal oxides to metal chlorides at elevated temperatures
complete dehydration of mellitic acid (benzenehexacarboxylic
(300 500 C). It is thermodynamically unstable with respect
acid). Oxocarbon anions, Cn On 2 , with apparent aromatic
to hydrolysis, but is kinetically very inert to hydrolysis because
properties are also known.20,21 The properties of these
of the absence of empty acceptor orbitals (e.g. d orbitals) for
carbon oxygen compounds are summarized below.
nucleophilic attack. However, heating carbon tetrachloride
with free alkali metals or other strong reducing agents can
lead to dangerous explosions. 4.1 Carbon Monoxide
Organic compounds containing only carbon and chlorine
+
are called chlorocarbons. The presence of relatively large Carbon monoxide, mp 205 C, bp 190 C, CO , is a
chlorine atoms on a carbon network makes the properties colorless, odorless, but very toxic gas that is sparingly soluble
of chlorocarbons very different than those of corresponding in water. Carbon monoxide is formed by burning carbon in a
hydrocarbons. In general, chlorocarbons with trigonal sp2 deficiency of oxygen. It therefore is a dangerous product of
carbon atoms are more stable than chlorocarbons with many combustion processes. Carbon monoxide is also made
tetrahedral sp3 carbon atoms. As a result, certain chlorocarbons by the water gas reaction from steam and coal as synthesis
having only sp2 carbon atoms, for example, perchlorofulvene gas, a 1:1 CO/H2 mixture arising from equation (5) at elevated
and perchlorofulvalene, are very stable under normal temperatures. On the laboratory scale, pure carbon monoxide
conditions, whereas their hydrocarbon analogs polymerize may be generated by the acid dehydration of formic acid,
rapidly. Chlorocarbon free radicals1 with trivalent carbon HCO2 H, using concentrated sulfuric acid. Transition metals
atoms are among the most stable carbon free radicals. For combine with carbon monoxide to form metal carbonyls,
example, the trivalent carbon atom in (C6 Cl5 )3 C is stable not which play a key role in vast areas of organometallic
only to air but even to permanganate oxidation. and coordination chemistry (see Metal Carbonyls; Carbonyl
Carbon tetrabromide is a pale yellow water-insoluble solid, Complexes of the Transition Metals, and Carbonylation
mp 90.1 C, bp 189.5 C. Carbon tetraiodide is a bright red Processes by Homogeneous Catalysis). The toxicity of carbon
solid which decomposes readily to I2 and I2 C=CI2 , again monoxide is a consequence of its binding to the iron in
indicating the stability of sp2 carbon atoms relative to sp3 blood hemoglobin, thereby inhibiting the essential function
carbon atoms in halocarbons (other than fluorocarbons). of hemoglobin as an oxygen carrier. Carbon monoxide can
Carbon tetraiodide is made by an electrophilic halogen bond to transition metals as a terminal or a bridging ligand
exchange reaction (equation 4).17 The increasing instability (Figure 1). Simple, neutral binary-metal carbonyls are volatile
of the carbon tetrahalides with increasing atomic weight of the covalent compounds, which readily decompose on heating to
halogen relates to the steady decrease in C X bond energies carbon monoxide and the free metal, and thus are often useful
from 485 kJ mol1 for the CF bond to 213 kJ mol1 for the sources of finely divided and/or pure metals such as chromium,
CI bond. molybdenum, iron, and nickel. Carbon monoxide reacts with
AlCl3
alkali metals to give the so-called alkali metal carbonyls, which
CCl4 + 4EtI CI4 + 4EtCl (4) contain salts of the acetylenediolate ion, OCCO ; on
4 CARBON: INORGANIC CHEMISTRY
O 4.4 More Complicated Carbon Oxides
+ +
M C O M C O M C O
Some more complicated carbon oxides are known with
M M carbon backbones familiar in organic chemistry. An example
is benzenehexacarboxylic acid (mellitic acid) trianhydride,
Figure 1 The bonding of CO to transition metals in metal carbonyls C12 O9 = C6 [(CO)2 O]3 (1), a white sublimable solid obtained
as terminal and bridging ligands by dehydration of the corresponding acid with acetyl chloride
in a sealed tube at 160 C.
2H2O
h
O O
H2 C=CH2 + C=C=O H2 C=C=CH2 + CO (7) OH O OH OH O OH
O O
O O O X X O OH
M OH O OH OH
M M M M M O O
M
O O O O O
Deltic acid Squaric acid Croconic acid Rhodizonic acid
h2-CO2 h1-CO2 mh1,h2-CO2 pKa 2.6 pKa 0.5 pKa 0.7 pKa 4.4
Colorless Colorless Yellow Red
R = Me, etc.
Ln M(CS) + R2 N [Ln MC(=S)MR2 ] (13) -C3 S5 subunit, respectively (Figure 6). Specifically, C3 S7 ,
C3 S8 , C6 S10 , and C6 S12 are based on the -C3 S5 subunit,
while C5 S7 contains the -C3 S5 subunit. In case of C6 S8 , two
6.3 More Complicated Carbon Sulfides isomers have been obtained, one of which is based on the
-C3 S5 subunit.
Besides carbon sulfides CS and CS2 , described in previous
sections, some other binary compounds of sulfur and carbon
have been known for a long time, such as C3 S2 and the
two isomers of C4 S6 and C9 S9 . In the latter, extensive
7 CYANIDES AND RELATED COMPOUNDS
delocalization leads to the formation of disulfide bonds
within linear three-sulfur sequences, and the molecule is
sometimes considered to be a carbon sulfur analogue of 7.1 Cyanogen
coronene (Figure 5).35
In addition, potential application of materials containing Cyanogen, NCCN , is a flammable and toxic gas,
carbon sulfur bonds in electronic industries has recently mp 28 C, bp 21 C, which is kinetically stable but
provided an impetus for the synthesis of further binary carbon endothermic (297 kJ mol1 ). It has a linear structure with
sulfides, leading to the discovery and characterization of C3 S7 , a sufficiently weak CC bond to allow dissociation into CN
C3 S8 , C5 S7 , C6 S8 , C6 S10 , and C6 S12 .36 The syntheses of the radicals. Cyanogen can be prepared by various oxidation
sulfides involve the dithiolate complex of a transition metal reactions of cyano derivatives. Thus, cyanogen is obtained
ion as a precursor and are based on the oxidative coupling from the oxidation of hydrogen cyanide (see below) with
and electrophilic sulfiding (e.g. via S2 Cl2 ) of either the - oxygen over a silver catalyst, with chlorine over activated
or -C3 S5 2 anion (Figure 6) and, consequently, molecular carbon or silica, or with nitrogen dioxide over CaO/glass.
structures of such compounds are based on either the - or Cyanogen is also obtained by oxidation of an aqueous
S S
S
S S S S S S
S S S S
S
S S S S S
S
S S S S S
S
S S S S S
S S S S S S S
S S
S
S S S S S
S S S S S S
S S S S S S
S S S S S S
S S S S S
S
(g) (h) (i)
Figure 6 Schematic representation of (a) -C3 S5 anion, (b) -C3 S5 anion, (c) C3 S7 , (d) C3 S8 , (e) C5 S7 , (f ) one of two isomers of C6 S8 ,
(g) the isomer of C6 S8 based on the -C3 S5 unit, (h) C6 S10 , and (i) C6 S12
CARBON: INORGANIC CHEMISTRY 7
include the trimer aminomalononitrile and the tetramer these metals. Organic isocyanides, RNC (R = alkyl or
diaminomaleonitrile (Figure 8). aryl group), also form an extensive series of transition
metal complexes, including zerovalent derivatives such as
Pt catalyst (PhNC)6 Cr; as in the case of metal cyano complexes, the
CH4 + NH3 HCN + 3H2 (16)
1200 C transition metal always bonds to the carbon rather than the
H = 247 kJ mol1 nitrogen atom of isocyanides.37
H2N N NH2
H2N
OH/80C NH3,
2H2N N N N N
+H2NC N
H2N CN
NH2
Cyanamide Dicyandiamide Melamine
(monomer) (dimer) (trimer)
pressure (equation 19). The NH3 and CO2 produced in this (O=C(NH2 )2 ), which was first found in the early nineteenth
reaction can be recycled to make more urea starting material. century, is regarded as the first link between inorganic and
organic chemistry.
1000 C
CaC2 + N2 CaNCN + C (18) KCN (aq) + PbO (aq) Pb (s) + KOCN (aq) (20)
H = 297 kJ mol1
heat
300 C Na2 CO3 + 2O=C(NH2 )2 2NaOCN + CO2 + 2NH3 + H2 O (21)
6H2 NC(=O)NH2 6NH3 + 3CO2 + C3 N3 (NH2 )3 (19) dry
100 atm
HOCN + H2 O NH3 + CO2 (22)
obtained by reaction of HCN with Cl2 or by electrolysis The thiocyanate ion,36 S =C=N , also called the
of an aqueous solution containing HCN and NH4 Cl. It rhodanid ion in the early German literature because of
readily undergoes trimerization to give cyanuric chloride, the intense red color of its FeIII derivative, is obtained by
C3 N3 Cl3 , which has a similar 1,3,5-triazine structure to the fusion of alkali metal cyanides with sulfur. It is also
melamine (Figure 9). The chlorine atoms in cyanuric chloride the product of the detoxification of the cyanide ion in living
are reactive toward nucleophilic substitution. Fluorination of systems. Most thiocyanate salts are very soluble in both water
cyanuric chloride gives cyanuric fluoride, C3 N3 F3 , which can and liquid ammonia and are useful soluble sources of metal
be cracked thermally to give cyanogen fluoride, FCN , bp ions in liquid ammonia. Thiocyanogen, NCSSCN , is
46 C, which polymerizes at room temperature. Cyanogen the prototypical example of a pseudohalogen, that is, a group
bromide, mp 52 C, bp 61.4 C, and cyanogen iodide, mp of atoms that behaves like a halogen, X2 (X = Cl, Br, I).
147 C, are volatile solids that can be made by treatment Thiocyanogen is made by bromination of a metal thiocyanate
of cyanide ion with the free halogen in aqueous solution. in an inert (nonprotonic) solvent (equation 23). Thiocyanogen
Cyanogen iodide can also be obtained from Hg(CN)2 and I2 . is rapidly hydrolyzed by water and rapidly and irreversibly
polymerized in the pure state. However, it can be handled in
solutions in inert solvents including glacial acetic acid, as well
7.6 Cyanic Acid and Cyanates as carbon tetrachloride or carbon disulfide.
The cyanate ion, O=C=N , like the cyanamide dianion, 2AgSCN + Br2 2AgBr + NCSSCN (23)
is isoelectronic and isostructural with carbon dioxide, and
is made by the mild oxidation of aqueous cyanide ion Selenocyanates are also known; they are analogous to
(equation 20). Sodium cyanate can also be made by heating thiocyanates but are less stable.
sodium carbonate with urea in the absence of a solvent
(equation 21). Unstable free cyanic acid (HOCN, bp 23.5 C,
Ka = 1.2 104 ) can be obtained by hydrolysis of cyanuric 7.8 Fulminic Acid
chloride (see above) to cyanuric acid, 1,3,5-trihydroxy- +
Fulminic acid, CNOH C=NOH, is a divalent
1,3,5-triazine, C3 N3 (OH)3 , followed by pyrolysis. Cyanic
acid undergoes facile hydrolysis in aqueous solution to carbon derivative like carbon monoxide; it is formally an
give carbon dioxide and ammonia (equation 22). In covalent oxime of carbon monoxide. Free fulminic acid is unstable,
derivatives or metal complexes, cyanate can bond either but the explosive mercury salt, which is used as a detonator,
through oxygen (cyanates) or nitrogen (isocyanates), thereby is obtained by treatment of elemental mercury with a mixture
+
providing examples of linkage isomerism.38 The facile of ethanol and nitric acid. The fulminate ion, CNO, like
isomerization of ammonium cyanate (NH4 + OCN ) to urea carbon monoxide and cyanide ion, functions as a strong-field
CARBON: INORGANIC CHEMISTRY 9
ligand toward transition metals to form complexes such as with n 2 can exist as different isomers. Specifically, the cis-
Fe(CNO)6 4 analogous to the ferrocyanide ion, Fe(CN)6 4 . or trans- positioning of substituents on bridgehead carbon
However, fulminato metal complexes, like mercury fulminate, atoms leads to two structurally distinct molecular types,
are frequently explosive. The likewise explosive silver the more strained being the one with substituents in trans-
fulminate (AgCNO) and silver cyanate (AgOCN) are of positions. Further possibilities of isomerism in [3]-ladderane
historical interest in being the first pair of isomers discovered, and higher members of the family arise from the possibility of
and they led to the first proposal of the concept of isomerism a nonterminal cyclobutane ring adopting either the anti or syn
(Liebig, 1823).39 configuration (Figure 11).
8.2 Significance
8 CARBON-BASED MOLECULAR LADDERS
The [n]-ladderane framework has gained additional
theoretical interest. The framework has been discovered in
Structures resembling a ladder are encountered in the biology and has been recognized as a potentially useful
chemistry (e.g. Zintl phases) of many elements, but among building block in materials science. These developments have
group IV elements are found only in the case of carbon.40 The provided an impetus for synthetic methods to construct [n]-
molecular ladders of carbon chemistry are [n]-ladderanes,41 ladderanes to be advanced.
small molecules built up of n edge-fused four-membered
rings, with n 1 (Figure 10). The four-membered rings in
[n]-ladderanes generally contain only carbon atoms, although 8.3 Theoretical
derivatives involving nitrogen are known.42
Most recent quantum chemical calculations involving [n]-
ladderanes suggest a defect in the ladderane framework, in the
8.1 Strain and Isomerism form of an olefin pair, can result in fluxional molecules named
sigmatropic shiftamers.44,45 The fluxional nature would stem
The simplest member of the class is the [1]-ladderane, a
from the ability of the olefin pair to travel across the defective
small and familiar strained molecule known as cyclobutane.
ladderane framework via a series of Cope rearrangements
The strain in a [n]-ladderane increases with the number
(Figure 12). Calculations predict the fluxionality of the
of fused rings and the introduction of multiple bonds.43
molecules depends on the size of the framework. Specifically,
The [2]-ladderane derivative, Dewar benzene, is highly
[n]-ladderanes with n > 7 are expected to be fluxional at and
unstable and converts readily to the conjugation-stabilized
above room temperature.
counterpart, benzene. Depending on the stereochemistry of
bridgehead atoms in the fused-ring system, [n]ladderanes
8.4 Biochemistry and Materials Science
H H
Biomolecules containing [3]- and [5]-ladderanes have been
H n H
discovered within intracellular lipid membranes of anammox
bacteria46 that recycle atmospheric nitrogen. The ladderane
Figure 10 Schematic representation of a [n]-ladderane lipids are found in the membrane surrounding a unique
cytoplasmic organelle, the anammoxosome, within which
the anaerobic oxidation of ammonia into molecular nitrogen
H H
occurs. The oxidation, known as the anammox process, follows
the reaction (equation 24):
CO R R R
OC CO R R R
Fe Ce(IV)
R
n
R R R
n = 05
(1ac) (2ac)
(a) R = H
(b) R = COOH
(c) R = COOCH3
conjugated polyenes in the same molecule, while the second in solution, single isomers of the [3]- and the [5]-ladderane are
one is intermolecular, relying on the reaction between two obtained in excellent yields (100% and 80%, respectively).55
molecules. The second approach requires the reactants to be Using the second approach, [3]-ladderane has been
highly organized and, so far, has been applied only in the solid synthesized using arene-perfluoroarene interactions to bring
state. reactant polyenes together in the crystal (Figure 16). The
The first approach has been pioneered by Hopf and reaction yields are low (20 25%) and limited by the
coworkers by covalently attaching polyene chains onto a breakdown of the crystal as the reaction proceeds.56
rigid molecular fragment, a [2.2]-paracyclophane.54 The Most recently, the methods of template-directed solid-
paracyclophane scaffold serves as a template to hold the state synthesis57 were employed to construct the [3]- and
two polyenes in the vicinity for a sequential [2 + 2] the [5]-ladderane. The construction involved a resorcinol
photodimerization. The covalent attachment of the polyene derivative (5-methoxyresorcinol) as a linear template to
chains onto the cyclophane effectively makes the dimerization organize pyridine-substituted polyenes for the reaction within
an intramolecular process (Figure 15). Upon UV-irradiation discrete molecular assemblies in solids. The assemblies are
hn, solution
COOH
COOH
COOH
COOH
F
F F F
F R
F F
F F R
hn, solid F
R F F F
F F
F
F F R F
F
R = H, CH3, OCH3
N
N HO (1) hn, solid
(2) Template removal
(a)
N
N H O
(1) hn, solid
(2) Template removal
(b)
Figure 17 Template-directed solid-state synthesis of the [3]- (a) and the [5]-ladderane (b)
12 CARBON: INORGANIC CHEMISTRY
held together via OH N hydrogen bonds between hydroxyl 11. D. H. Parker, P. Wurz, K. Chatterjee, K. R. Lykke, J. E. Hunt,
groups of the template and pyridine nitrogen atoms of the M. J. Pellin, J. C. Hemminger, D. M. Gruen, and L. M. Stock,
reactant (Figure 17). While the liaison between the template J. Am. Chem. Soc., 1991, 113, 7499.
and the reactant is based on a noncovalent interaction, the 12. W. A. Sheppard and C. M. Sharts, Organic Fluorine
intermolecular nature of the photodimerization is retained. Chemistry, Benjamin, New York, 1969.
Upon UV-irradiation of each assembly in the solid, single 13. M. Hudlicky, Organic Fluorine Chemistry, Plenum Press,
isomers of the [3]- and the [5]-ladderane were obtained in New York, 1971.
100% yield.58 14. M. Hudlicky, Chemistry of Organic Fluorine Compounds,
Ellis Horwood, Chichester, 1976.
15. R. E. Banks, Preparation, Properties, and Industrial
Applications of Organofluorine Compounds, Ellis Horwood,
9 RELATED ARTICLES Chichester, 1982.
16. J. G. Riess and M. Le Blanc, Pure Appl. Chem., 1982, 54, 2383.
Carbides: Transition Metal Solid-state Chemistry; Carbon: 17. M. Hargittai, G. Schultz, P. Schwerdtfeger, and M. Seth, Struct.
Fullerenes; Carbonyl Complexes of the Transition Metals; Chem, 2001, 12, 377.
Carbonylation Processes by Homogeneous Catalysis; Cyanide 18. M. J. Parkington, T. A. Ryan, and K. R. Seddon, J. Chem. Soc.,
Complexes of the Transition Metals; Intercalation Chemistry. Dalton Trans., 1997, 251.
19. T. A. Ryan, C. Ryan, E. A. Seddon, and K. R. Seddon, in
Phosgene and Related Carbonyl Compounds, Topics in
Inorganic and General Chemistry, Monograph 24, ed.
10 FURTHER READING R. J. H. Clark, Elsevier Science B. V., Amsterdam, 1996.
20. R. West, ed., Oxocarbons, Academic Press, New York, 1980.
A. A. Newman ed., Chemistry and Biochemistry of Thiocyanic Acid 21. D. Braga, L. Maini, and F. Grepioni, Chemistry A European
and its Derivatives, Academic Press, London, 1975. Journal, 2002, 8, 1804.
A. G. Sharpe, The Chemistry of Cyano Complexes of the Transition 22. M. E. Volpin and I. S. Kolomnikov, Organometal. React.,
Metals, Academic Press, London, 1976. 1975, 5, 313.
23. R. Eisenberg and D. E. Hendriksen, Adv. Catal., 1979, 28, 79.
24. J. A. Ibers, Chem. Soc. Rev., 1982, 11, 57.
25. D. J. Darensbourg and R. A. Kudaroski, Adv. Organometal.
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36. C. P. Galloway, D. D. Doxsee, D. Fienske, T. B. Rauchfuss,
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S. R. Wilson, and X. Yang, Inorg. Chem., 1994, 33, 4537.
Chemical Society, Washington, DC, 1992, ACS Symposium
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CARBON: INORGANIC CHEMISTRY 13
39. W. Bock, Eur. J. Inorg. Chem., 2003, 4275. 49. W. Li and M. A. Fox, J. Am. Chem. Soc., 1996, 118, 11752.
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Chem. Soc., 1994, 116, 3645.
Carbonyl Complexes of the +
C O C O
Transition Metals (1)
1 INTRODUCTION
Carbon monoxide forms binary combinations with
transition metals. Well-established examples are the metal
Metal carbonyls are compounds containing one or more carbonyls of the 3d series: V(CO)6 , Cr(CO)6 , Mn2 (CO)10 ,
MCO bonds, where M is a transition metal, that is, an element Fe(CO)5 , Co2 (CO)8 , Ni(CO)4 .
possessing an incomplete d shell, of electronic configuration When carbon monoxide is bonded to a transition element,
dn (0 < n < 10). However, there are some examples of in a positively charged or even uncharged compound,
compounds of this class containing metals with a completely the electrophilic capacity of carbon increases compared
filled (d10 ) or an empty (d0 ) shell.15 A few carbonyl with the isolated molecule. Examples of nucleophilic
derivatives are also known for lanthanide6 and actinide7 attack are in equations (4) and (5). The reaction of
cations, of 4f and 5f electronic configuration, respectively. methyl lithium with W(CO)6 giving the anionic acyl
Outside the d and f transition series, carbonyl derivatives have complex of equation (4a) is followed by alkylation to
been reported, the best described examples being those of the carbene derivative of equation (4b). The formation of
boron(III), which have been crystallographically established, a carbamoyl complex with cis-PtCl2 (CO)2 is shown in
with CO s at 2176 cm1 for B(BCl2 )3 (CO)8 and at 2251 cm1 equation (5).
for B(CF3 )3 (CO).9 Moreover, unstable combinations with CO,
such as Be(CO)n 10 and B4 (CO)2 11 are known for main group W(CO)6 + LiMe Li[W(CO)5 C(O)Me] (4a)
elements, as prepared by the metal vaporization technique, Me3 O +
that is, by contacting carbon monoxide with the metal vapor Li[W(CO)5 C(O)Me] W(CO)5 C(OMe)Me (4b)
quenched in a solid matrix around 20 K or lower.10,11 cis-PtCl2 (CO)2 + 2R2 NH NH2 R2 [cis-PtCl2 (CO)C(O)NR2 ] (5)
Carbon monoxide is the product of partial combustion
of carbon, the Hf0 being 110.4 kJ mol1 . Its enthalpy
of dissociation (1073 kJ mol1 ) is the highest known for
a diatomic molecule. In agreement with the oxidation 2 SYNTHESIS
state +II for carbon, CO can be prepared by a syn-
proportionation reaction (G0 = +120.1 kJ mol1 ), favored
2.1 Generalities
at high temperature (equation 1).
Binary metal carbonyls span a wide range of oxidation
C(s) + CO2 (g)
2CO(g) (1) states from positive,14 for example, +III in [Ir(CO)6 ]3+ , to
2 CARBONYL COMPLEXES OF THE TRANSITION METALS
negative,15,16 for example, IV in [M(CO)4 ]4 (M = Cr, Mo, 2.1.1 The Reducing Agent
W). Interesting cases of intermediate oxidation states are the
hexacarbonyl metalates(II)1719 of the group 4 metals (Ti, Reduction of a readily available inorganic compound is usu-
Zr, Hf ) of formula [M(CO)6 ]2 . Some relevant examples of ally required to prepare the corresponding carbonyl derivative.
anionic, neutral, and cationic binary metal carbonyls are listed The choice of the reducing agent is usually the most critical
in Table 1. point in the synthesis. Sometimes, no additional reducing
In practice, nickel is the only metal which, when agent is necessary, when CO plays this role. The oxida-
activated and finely divided, can be converted into the tion products are CO2 (G0f = 394 kJ mol1 ) or COCl2
corresponding carbonyl Ni(CO)4 under mild conditions (G0f = 206 kJ mol1 ), if the starting material is a metal
of temperature and pressure (equation 6). This compound, oxide or a metal chloride, respectively. The reductive carbony-
discovered20 by Mond and coworkers, has played an lation is mostly used with metal oxides and metal chlorides
of a covalent nature, that is, in relatively high oxidation
important role in both the development of nickel-catalyzed
states. Decacarbonylditechnetium(0) and decacarbonyldirhe-
organic syntheses13 and in the technical manufacture of
nium(0) can be prepared by heating NH4 [MO4 ], M = Tc, Re,
nickel.
with carbon monoxide under pressure at high temperature, the
reducing agent being CO, with the possible participation by
Ni(s) + 4CO(g) Ni(CO)4 (g) (6)
the ammonium cation, vide infra.
Molecular hydrogen can be used as a reducing agent in the
Important aspects of the synthesis of metal carbonyls by presence of CO; the equimolar CO/H2 synthesis gas mixture
reductive ligation (see Reductive Ligation) are (a) the reducing is employed to reduce metal carboxylates (equation 7). Metal
agent; (b) the reaction medium; and (c) the pressure of CO alkyls or aryls, such as Grignard reagents (see Grignard
and the temperature. Reagents), lithium alkyls or aryls, and aluminum alkyls, have
CARBONYL COMPLEXES OF THE TRANSITION METALS 3
been used for the preparation of metal carbonyl derivatives. Reviews have appeared on preparative and structural
With a metal chloride as the starting material, ligand exchange aspects of metal carbonyls.2225
occurs, followed by reduction due to homolytic cleavage of
the metal carbyl (alkyl or aryl) bond.
2.2 Group 6
n
M(O2 CR)n + mCO + H2 nRCO2 H + M(CO)m (7) The neutral mononuclear carbonyls of this group have
2
the formula M(CO)6 (M = Cr, Mo, W) (see Table 1).
Electropositive metals characterized by low standard Hexacarbonylchromium(0) can be prepared by treating
reduction potentials (alkali metals, Mg, Zn) have been anhydrous CrCl3 with the phenyl Grignard reagent PhMgBr
frequently used for the reduction of transition metal halides in in THF with CO under pressure at temperatures between
the presence of carbon monoxide. The finely divided reducing 4 and +10 C. The intermediacy of the chromium(III)
metal is previously activated by one of the conventional derivative CrPh3 (THF)3 in this process has been claimed. A
methods. Ethers are frequently used as reaction media. hydrolytic step is required to obtain Cr(CO)6 , which suggests
The reduction may be accompanied by secondary reactions that chromium under the reaction conditions is possibly
with formation of carbon carbon bonds (see equation 8). converted to MgPh+ [Cr(CO)5 C(O)Ph] . Another preparation
The products with n = 2 contain the acetylenediolate anion of Cr(CO)6 involves the reductive carbonylation of several
[C2 O2 ]2 , the sodium, potassium, rubidium, and cesium chromium(III) salts under CO pressure (100 300 atm) at
derivatives being isotypical; the reaction of CO with a 130 180 C in pyridine as the medium; both magnesium and
potassium melt leads to the product with n = 6, containing zinc are used as reductants. Pyridine is essential for this
the anion of hexahydroxybenzene, [C6 O6 ]6 .21 reaction, and zinc and magnesium have a synergic effect;
presumably, the formation of the pyridine radical anion is
nCO + ne [(CO)n ]n (8) important for the reduction.23
The hexacarbonyls of chromium, molybdenum, and
tungsten can be prepared by reacting a metal salt with AlR3 in
2.1.2 The Reaction Medium the presence of CO; yields as high as 92% (Cr), 76% (Mo), and
92% (W) are obtained. Anhydrous CrCl3 can be reduced by
In dry methods, no solvent is used. In wet methods,
Al/AlCl3 in benzene at 140 150 C under a CO pressure. The
an anhydrous organic solvent is employed, normally
intermediacy of the [Cr(C6 H6 )2 ]+ cation, which is the primary
hydrocarbons or ethers. Exceptionally, in the case of the
product of the reaction in the CrCl3 /Al/AlCl3 /benzene system
carbonyl derivatives of palladium(II), platinum(II), and
in the absence of CO, has been suggested in the carbonylation
gold(I), thionyl chloride is used as solvent, as it provides
process.23
the rigorously anhydrous conditions for the survival of the
reaction product. In certain cases, water can also be used as
the reaction medium with or without the addition of a specific 2.3 Group 7
reducing agent. In the latter case, CO is the reducing agent and
carbonate is the corresponding oxidation product. Reducing Decacarbonyldimanganese(0), Mn2 (CO)10 , was originally
agents such as Na2 S2 O4 or formamidinesulfinic acid have also prepared from MnI2 , Mg, Cu, and CuI in Et2 O under CO
been used. pressure (200 atm) at room temperature. The best method
available for the preparation of Mn2 (CO)10 is the alkylation
of anhydrous manganese(II) acetate with AlR3 in i-Pr2 O
2.1.3 Temperature and Pressure of CO
under CO pressure at 60 140 C. A synthesis operating at
The preparative procedures reported in the literature atmospheric pressure of CO uses the methylcyclopentadienyl
usually require high temperature (50 200 C) and pressure derivative of manganese(I), Mn(MeC5 H4 )(CO)3 , which is
(50 300 atm). On a laboratory scale, attention has been reduced by sodium in diglyme (16 20% yield).23
paid to design new preparative methods operating at ambient Decacarbonylditechnetium, Tc2 (CO)10 , requires some
or slightly higher temperature and atmospheric pressure for special precautions since technetium is a -emitter. Tc2 (CO)10
safety reasons and for avoiding the use of expensive stainless has been proposed as the starting material for the preparation
steel autoclaves. The solubility of CO in the reaction medium of technetium compounds with potential radiopharmaceutical
increases with pressure; in organic solvents, the concentration properties.26 The original method of preparing Tc2 (CO)10
of CO in solution is about 7 103 M at atmospheric pressure. consists of treating the heptoxide, Tc2 O7 , with CO under
The rate of reduction of the metal species must match the rate pressure (250 350 atm) at 220 275 C (equation 9; M =
of transfer of CO from the gas phase to the solution, and Tc).23
efficient stirring is therefore essential. Methods of preparation
that use mild reaction conditions will be specifically noted in M2 O7 + 17CO 7CO2 + M2 (CO)10 (9)
the following subsections. M = Tc, Re
4 CARBONYL COMPLEXES OF THE TRANSITION METALS
with syngas (1:1, CO/H2 ) at high temperature and pressure in 80 230 C the product is Rh6 (CO)16 . This is consistent
a hydrocarbon solvent (see equation 17 for the carboxylate). with an endothermic equilibrium from the tetramer to the
When a Lewis base is used as solvent and preformed Co2 (CO)8 hexamer (equation 22). A two-step synthesis of Rh4 (CO)12
is introduced, excellent yields of Co2 (CO)8 are obtained at at room temperature and atmospheric pressure involves the
30 C and 180 atm of H2 (100 atm) and CO (80 atm).23 reduction of the [RhCl6 ]3 anion to [RhCl2 (CO)2 ] with
In the synthesis of octacarbonyldicobalt(0), an important copper, followed by reduction with water and CO in the
by-product is the hydride CoH(CO)4 , which is promptly presence of a sodium citrate buffer. The yields are nearly
decomposed to Co2 (CO)8 by adventitious oxygen or quantitative.23
spontaneously (equation 18) (see Hydride Complexes of the
Transition Metals). 3
2
Rh4 (CO)12
Rh6 (CO)16 + 2CO (22)
Table 2 Carbonyl stretching vibrations of the metal carbonyl clusters are also known (see Polynuclear
tetracarbonyls of group 10 Organometallic Cluster Complexes).50
The principal bonding arrangements of carbon monox-
Compound CO (cm1 ) kCO (mdyn A1 )
ide are (a) terminal (2); (b) doubly bridging (3), and
Ni(CO)4 2052 17.23 (c) triply bridging (4) (see Bridging Ligand). In polynuclear
Pd(CO)4 a 2070 17.55 metal carbonyl clusters where the metal atoms define a poly-
Pt(CO)4 a 2053 17.28
hedron, doubly bridging carbonyl groups are also called
a
Prepared from the metal vapor in a CO matrix at edge-bridging, whereas face-bridging is synonymous with
about 20 K. triply bridging ligands. The terminal MCO bond is nearly
linear. Table 3 contains the structural features of some relevant
metal carbonyls.
At variance with the easy accessibility of Ni(CO)4 , the cor-
responding tetracarbonyls of palladium(0) and platinum(0),
Pd(CO)4 and Pt(CO)4 , have been identified only spectro- O O
scopically (IR) at low temperature, both being prepared by CO C C
vaporization of the metal followed by reaction with CO in M M M M M
a solid matrix at about 20 K. These compounds decompose M
at higher temperature. Table 2 shows the IR spectroscopic (2) (3) m2-CO (4) m3-CO
properties of the tetracarbonyls of nickel, palladium, and plat-
inum, as obtained by vaporization of the corresponding metal,
measured under the same experimental conditions. The com- 3.1 Group 6
pounds show one carbonyl stretching vibration, as expected
for the tetrahedral geometry. The values of CO and the CO The hexacarbonyls of chromium, molybdenum, and
force constant of Pd(CO)4 are higher than those of both tungsten are mononuclear; the internal bonding parameters
Ni(CO)4 and Pt(CO)4 (see Section 7).4143 Attempts have are presented in Table 3. The coordination geometry is
been made44 to isolate the tetracarbonyl of platinum(0) by that of a regular octahedron of idealized Oh symmetry.
carbonylation of some olefin complexes of platinum(0), in The crystal packing is due to weak van der Waals
particular, the norbornene derivative Pt(C7 H10 )3 . The reac- interactions (see van der Waals Forces), which explains
tion, carried out in toluene as solvent and at room temperature the volatility of these compounds (the vapor pressures of
or lower, was monitored gasvolumetrically and shown to lead Cr(CO)6 , Mo(CO)6 , and W(CO)6 at 30 C are 0.28, 0.27,
to an amorphous, insoluble, and unstable carbonyl derivative and 0.06 mmHg, respectively), and their solubility in organic
of platinum with a CO:Pt molar ratio of 2 under the best solvents.23
conditions. By using catalytic amounts of CO, the starting
olefin complex of platinum is converted to platinum metal at 3.2 Group 7
room temperature. These experiments show conclusively that
platinum(0)-carbonyl derivatives of low nuclearity are not sta- The decacarbonyls of manganese, technetium, and
ble even under the mild conditions used for the carbonylation rhenium, of formula M2 (CO)10 , have terminal carbonyl groups
experiments. and a metal metal bond. The molecular symmetry is D4d with
the two M(CO)5 fragments in a staggered conformation. The
heterodinuclear decacarbonyl MnRe(CO)10 is also known as
obtained by the redox reaction of a rhenium pentacarbonyl
3 MOLECULAR STRUCTURES halide with the pentacarbonylmanganate(I) anion at room
temperature (at 160 C or higher, the heterodinuclear carbonyl
tends to form the homodinuclear compounds with an
Uncharged mononuclear and polynuclear metal carbonyls
equilibrium constant close to the statistical value51 ). The X-
are known for the group 5 to group 10 metals. The
ray diffraction study of MnRe(CO)10 has shown the Mn Re
EAN rule (see Effective Atomic Number Rule) is normally
distance of 2.909 A to be shorter than the sum of the
obeyed, so elements with an even atomic number form
covalent radii obtained from the homodinuclear compounds
mononuclear compounds, for example, Cr(CO)6 , Fe(CO)5 ,
(Table 3).
and Ni(CO)4 , while elements with an odd atomic number
form dinuclear compounds, for example, Mn2 (CO)10 and
Co2 (CO)8 , containing metal metal bonds. 3.3 Group 8
Especially with 4d and 5d elements, polynuclear
compounds with metal metal bonds (metal carbonyl The molecular structure of Fe(CO)5 , determined on the
clusters;4549 see Cluster) are formed under reduced carbon solid compound below its freezing point (20.5 C) by X-
monoxide pressure and/or high temperature. Heteronuclear ray diffraction, is trigonal bipyramidal (D3h symmetry). An
CARBONYL COMPLEXES OF THE TRANSITION METALS 7
electron-diffraction study showed a significant difference in atoms at a bond distance of 2.848 A (Ru) or 2.88 A (Os). All
the FeCO bond distance between the axial and the equatorial carbonyl groups are terminal.
carbonyl groups (see Table 3).
Fe2 (CO)9 is a sparingly soluble molecule in most organic
inert solvents; the molecule contains three bridging carbonyl
3.4 Group 9
groups connecting the two Fe(CO)3 units, and it can
be described as (OC)3 Fe(2 -CO)3 Fe(CO)3 . The iron iron
distance is 2.523 A, according to an X-ray diffraction study.24 The dinuclear Co2 (CO)8 52,53 has a solid-state structure
Fe3 (CO)12 is a trinuclear compound that contains two sets of with two doubly bridging carbonyl groups; each cobalt atom
nonequivalent iron atoms: one iron atom is hexacoordinated to is hexacoordinated to three terminal carbonyl groups, to the
four terminal carbonyl groups and to the other two iron atoms, other cobalt atom, and to two bridging carbon atoms, that
the rest of the molecule being (OC)3 Fe(2 -CO)2 Fe(CO)3 with is, (OC)3 Co(2 -CO)2 Co(CO)3 . The cobalt cobalt distance is
terminal and bridging carbonyl groups. The carbonyl bridges 2.530 A (or 2.528 A in the independent molecule). Within the
are not symmetrical. terminal carbonyl groups, the MCO bond distances differ
The pentacarbonyls of ruthenium(0) and osmium(0), significantly between axial and equatorial groups, as for an
M(CO)5 (M = Ru, Os), show two carbonyl stretching X-ray diffraction study at low temperature. A cobalt cobalt
vibrations in the IR spectrum (heptane) at 2035s, 1999vs interaction through the bridging carbonyl groups has been
(Ru) and 2034s, 1991vs (Os) cm1 . On the basis of the suggested on the basis of a charge-density study.53 In solution,
number of IR-active bands observed, a trigonal bipyramidal this molecule has been suggested to be in equilibrium
structure of D3h symmetry is suggested. with a form not containing bridging carbonyl groups (see
The isomorphous Ru3 (CO)12 and Os3 (CO)12 have a highly equation 25), and further with a third isomer. The G0 of the
symmetrical structure of D3h symmetry with equivalent metal reaction is about zero at room temperature, the equilibrium
8 CARBONYL COMPLEXES OF THE TRANSITION METALS
constant being about 1.54 A similar reaction (see equation 27) has been reported
for hexacarbonylvanadium(0).55 By these reactions, the
(OC)3 Co(2 -CO)2 Co(CO)3
(OC)4 CoCo(CO)4 (25) tetracarbonylcobaltate(I) and the hexacarbonylvanadate(I)
anions are generated. The crystal and molecular structure of
This group of elements forms numerous cluster the product of the disproportionation reaction of V(CO)6 with
systems.48,49 Dodecacarbonyltetracobalt, Co4 (CO)12 , has a tetrahydrofuran of formula [V(THF)4 ][V(CO)6 ]2 has been
tetrahedral arrangement of the four cobalt atoms. An apical shown56 to consist of vanadium(II) octahedrally surrounded
Co(CO)3 group is symmetrically coordinated by CoCo bonds by four thf s in the equatorial positions and by two axial
to a basal Co3 (CO)9 fragment consisting of three Co(CO)2 carbonyl oxygens from two hexacarbonylvanadate anions
groups joined by doubly bridging carbonyl groups and by a resulting in a linear VOCV sequence (see Isocarbonyl
cobalt cobalt bond, that is, Co4 (CO)9 (2 -CO)3 . Complexes).
In hexadecacarbonylhexacobalt(0), Co6 (CO)16 , the six
cobalt atoms define an octahedron. The compound is 3Co2 (CO)8 + 12L 2CoL6 [Co(CO)4 ]2 + 8CO (26)
isomorphous with Rh6 (CO)16 , whose structure is described 3V(CO)6 + 6L VL6 [V(CO)6 ]2 + 6CO (27)
below. L = Lewis base
Dodecacarbonyltetrarhodium(0), Rh4 (CO)12 , has essen-
tially the same structure as Co4 (CO)12 , that is, its structure can
be described as Rh4 (CO)9 (2 -CO)3 . 4.1 Substitutions
In hexadecacarbonylhexarhodium(0), Rh6 (CO)16 , the six
rhodium atoms form an octahedron. Each rhodium atom binds Substitution reactions may be carried out thermally,
two terminal carbonyl groups, the remaining four carbonyl photochemically, and chemically. In a thermal substitution,
groups being triply (face) bridging on four triangular faces of heat is used to both increase the kinetics of the process and shift
the octahedron, that is, Rh6 (CO)12 (3 -CO)4 . the equilibrium, especially when gaseous carbon monoxide is
At variance with the corresponding cobalt and rhodium produced, the S 0 of the reaction being normally positive.
analogs, dodecacarbonyltetrairidium(0), Ir4 (CO)12 , consists One of the more extensively studied substitution reactions
of a tetrahedron of four iridium atoms, each being bonded to of the hexacarbonyls of group 6 is the formation of the
three terminal carbonyl groups, no bridging carbonyl groups tricarbonylarenemetal(0) complexes (equations 28a), satisfac-
being present. tory conversions being obtained by removing the CO. The
Two isomeric forms of hexadecacarbonylhexairidium(0), tricarbonyl derivatives are converted into the hexacarbonyls
Ir6 (CO)16 , are known: a red isomer, isostructural with with CO at room temperature. For Mo(CO)3 (6 -arene), the
Rh6 (CO)16 , and a black isomer that has four edge-bridging carbonylation to Mo(CO)6 is accelerated by catalytic amounts
carbonyl groups rather than face-bridging. The structure of of iodine. This effect is explained by the formation of molyb-
the black isomer is described as Ir6 (CO)12 (2 -CO)4 . denum(II) carbonyl complexes (some of which have been
isolated and crystallographically established) containing ter-
minal iodide ligands that may act as catalysts in the substitution
3.5 Group 10 reaction.57
An electron-diffraction experiment in the gas phase and an
X-ray diffraction study at low temperature on solid Ni(CO)4 M(CO)6 + arene
M(CO)3 (6 -arene) + 3CO (28a)
have shown the compound to have a regular tetrahedral M = Cr, Mo, W
geometry. An accurate refinement of the structural data has
established the carbonyl ligands to be C-bonded to nickel.23
The tricarbonyl-6 -arene metal complexes of chromium,
molybdenum, and tungsten have a pseudooctahedral geometry
with the arene occupying the triangular face of the octahedron,
the opposite triangular face being defined by the three carbonyl
4 REACTIONS OF GROUPS 610 groups, usually in a staggered conformation (5).
Carbonyl substitution in the hexacarbonyls M(CO)6 (M = complexes of formula Ni(CO)4n (ER3 )n are known (see equa-
Cr, Mo, W) by the cyclopentadienyl anion gives the tricarbonyl tion 31). The tertiary phosphine complexes of nickel(0) are
Cp derivatives (equation 28b) important catalytic precursors, as in the trimerization of sub-
stituted acetylenes or in the dimerization of butadiene to
M(CO)6 + C5 H5 [M(CO)3 (5 -C5 H5 )] + 3CO (28b) cyclo-octa-1,5-diene.
Pentacarbonyliron(0) with butadiene gives the tricarbonyl MX(CO)5 + AlX3 + CO [M(CO)6 ]AlX4 (32)
derivative Fe(CO)3 (C4 H6 ). Cyclobutadienetricarbonyliron(0), M = Mn, Re; X = halide
Fe(CO)3 (C4 H4 ), is prepared by dehalogenation of cis-3,4-
dichlorobutene in the presence of Fe2 (CO)9 . This was the first
cyclobutadiene complex to be reported in the literature (see 4.2 Oxidations
equation 30).59
Neutral metal carbonyls frequently undergo oxidation by
air, and most of these compounds must be handled under
Cl an inert atmosphere. The derivatives of groups 6 and 7 are
Fe2(CO)9
Fe (30) sufficiently inert, and the corresponding solid products can
Cl OC CO be handled in air for short periods of time. In solution, metal
CO carbonyls may be oxidized by halogens, may be converted
by dihydrogen to the corresponding hydrido complexes, may
Several alkene complexes of iron(0) have been reported, react with alkyl halides and with substances containing active
of general formula Fe(CO)4 (alkene), where the alkene can protons. Frequently, oxidation of the central metal atom is
be ethylene, acrylonitrile, maleic anhydride, or methyl followed by partial or complete loss of the carbonyl ligands,
methacrylate. In these complexes, the original trigonal since the stability of the MCO bond generally decreases as
bipyramidal structure of the pentacarbonyl is retained with the oxidation state of the metal increases. Carbonyl derivatives
one of the equatorial positions now being occupied by the of metals in oxidation state II or higher are known primarily
alkene ligand. The tetracarbonyliron(0) complex of fumaric for the 4d and 5d metals of groups 6 10.
acid has idealized C2 symmetry and has been resolved into its Hexacarbonylchromium(0) is readily attacked by chlorine
two enantiomers.60 giving CrCl3 , CO, and COCl2 . Bromine and iodine do not
Isocyanides displace carbon monoxide from Fe(CO)5 , attack Cr(CO)6 to any substantial extent at room temperature.
yielding the tetracarbonyl and the tricarbonyl derivatives, The chromium tricarbonyl arene complexes, Cr(CO)3 (6 -
Fe(CO)4 (RNC) and Fe(CO)3 (RNC)2 , respectively. arene), are readily oxidized at room temperature by I2 to
Octacarbonyldicobalt gives substitution reactions with give CrI3 ; this is a convenient preparative method for the
some difficulty because this metal carbonyl frequently anhydrous iodide. Although the oxidation of the tricarbonyl
undergoes facile disproportionation (see Disproportionation) arene derivatives of chromium with I2 does not show evidence
(see equation 26), reduction, or oxidation reactions. With of intermediate carbonyl complexes in oxidation states >0,
diphenylacetylene, Co2 (CO)8 gives the substitution product the corresponding molybdenum(0) compounds give a series
Co2 (CO)6 (C2 Ph2 ). The molecular structure is directly derived of carbonyl iodides of molybdenum(II),57 for example, the
from that of the precursor, with the acetylenic ligand being ionic [Mo(CO)3 (6 -arene)]I.
almost perpendicular to the cobalt cobalt vector, thereby Hexacarbonylmolybdenum and -diketones yield the
replacing the two bridging carbonyl groups.23 molybdenum(III) chelate complexes as shown in equation (33)
Tetracarbonylnickel(0) is quite reactive and several sub- for acetylacetone.
stitution products are known. For example, with tertiary
phosphines and similar pnicogen-containing derivatives, many Mo(CO)6 + 3C5 H8 O2 6CO + Mo(C5 H7 O2 )3 + {3H} (33)
10 CARBONYL COMPLEXES OF THE TRANSITION METALS
Oxidation of the decacarbonyldimetal(0) compounds of homogeneous due to the formation of the naphthalene radical
manganese, technetium, and rhenium by halogens gives anion C10 H8 . Soluble reducing agents in hydrocarbons
the corresponding halopentacarbonylmetal(I) complexes (see include CoCp 2 , or the corresponding vanadium(II) species.
equation 34). In basic aqueous solution, coordinated carbon monoxide
can act as a reducing agent with carbonate being the oxidation
M2 (CO)10 + X2 2MX(CO)5 (34) product for the case of a mononuclear compound undergoing
M = Mn, Tc, Re a two-electron reduction (equation 39).
bipyramid; Td for [Fe(CO)4 ]2 , tetrahedron}.63 By forcing the on the complex. This is shown by the IR data for the following
reducing conditions, the tetracarbonylmanganato(III) and compounds with the CO of the main carbonyl stretching
the tetracarbonylchromato(IV) anions have also been vibration being reported in parenthesis (cm1 ): [Fe(CO)6 ]2+
obtained,15,16 thus expanding the isoelectronic series (2204), [Mn(CO)6 ]+ (2090), Cr(CO)6 (2000), [V(CO)6 ]
of the tetracarbonyl compounds: Ni(CO)4 , [Co(CO)4 ] , (1859), and [Ti(CO)6 ]2 (1748) for the isoelectronic series
[Fe(CO)4 ]2 , [Mn(CO)4 ]3 , [Cr(CO)4 ]4 . of the hexacarbonyls; Ni(CO)4 (2058), [Co(CO)4 ] (1883),
[Fe(CO)4 ]2 (1730), [Mn(CO)4 ]3 (1670), and [Cr(CO)4 ]4
Fe(CO)5 + 2Na Na2 [Fe(CO)4 ] + CO (44) (1462) for the isoelectronic series of the tetracarbonyl
derivatives.
The metal carbonyls of group 9 undergo reduction to the
tetracarbonylmetalates(I) (see equation 45 for Co2 (CO)8 ). +
M C O M C O
Acidification of an aqueous solution of Na[Co(CO)4 ] followed
(6)
by extraction into an organic solvent produces the hydride
CoH(CO)4 (see equation 46), which is a sufficiently strong
acid to be converted to the trialkylammonium derivative by The number of carbonyl bands increases as the overall
tertiary amines R3 N (R = Me, Et) (equation 47). The C3 symmetry of the molecule decreases. Only one IR-active
symmetry of CoH(CO)4 in the gas phase is maintained in carbonyl stretching vibration is normally observed for species
the trialkylammonium derivatives as shown by X-ray64 and of high symmetry, such as octahedral (Oh ) or tetrahedral
neutron-diffraction studies.65,66 (Td ) complexes (see the examples given above; the data for
the negatively charged species refer to media with a strong
Co2 (CO)8 + 2Na 2Na[Co(CO)4 ] (45) solvating power for the cation).
[Co(CO)4 ] + H +
CoH(CO)4 (46) In polynuclear metal carbonyls, the bonding modes (a),
(b), and (c) (see Section 3) are characterized by a decrease
of the carbonyl stretching frequency, in agreement with the
OC OC reduction of CO bond order from (a) to (c). For neutral
H compounds, CO values for bonding modes (a) (c) follow the
Co CO + NR3 R3N H Co CO
OC OC (47) trend: (a) 2200 1850, (b) 1850 1750, (c) 1750 1620 cm1 .
OC OC 13
C NMR spectra have been extensively used67 for analyt-
CoH, 1.56 CoH, 2.613(2)
ical and structural purposes in metal carbonyl chemistry.
NiCp(CO)4 + VCp(CO)4
[Mn(CO)5] V(h6-arene)2
e
Mn2(CO)10 + [V(CO)6] [V(h6-arene)2][V(CO)6]
[V(CO)6]
Table 4 Binary metal carbonyls of groups 4 and 5; crystal moment reduces considerably, and the compound becomes
structures substantially diamagnetic at the lowest temperature.71,72 An
X-ray diffraction study at 245 K73 shows the compound to be
Compound Space group MCOt (A)
isomorphous with the corresponding chromium analog (see
Group 4 Tables 3 and 4), thus confirming some earlier results.74,75 The
[Ti(CO)6 ]2a P 21 /n 2.038(3) coordination geometry around vanadium is octahedral with a
[Zr(CO)6 ]2a P 21 /n 2.210(4) marginally significant tetragonal distortion.
[Hf(CO)6 ]2a P 21 /n 2.178(3)
Group 5
Hexacarbonylvanadium(0) undergoes reduction to
V(CO)6 Pnma ax. 1.993(2) [V(CO)6 ] , oxidation to vanadium(I) complexes, or
eq. 2.005(2) disproportionation to vanadium(II) and vanadium(I) or to
[V(CO)6 ]b R 3 1.931(9) vanadium(I) and vanadium(I) in the presence of Lewis bases
[Nb(CO)6 ]b R 3 2.089(5) or aromatic hydrocarbons, respectively. The chemistry of
[Ta(CO)6 ]b R 3 2.083(6) V(CO)6 is shown in Scheme 1. Thus, hexacarbonylvanadium
behaves as an oxidizing agent toward a number of
a
As the [K(cryptand 2.2.2)]+ derivative. b As the
bis(triphenylphosphine)nitrogen(+), PPN+ , derivative. organometallic compounds, the driving force being the
formation of the 18-electron species [V(CO)6 ] . Reductions
of biscyclopentadienyl derivatives, such as NiCp2 and MnCp2 ,
vanadium(0), a low-spin d5 complex of formula V(CO)6 , is by V(CO)6 are also known. A chemical interaction was found
best prepared by the sequence shown in reaction (48) and in between VCp 2 , Cp* = 5 -C5 Me5 , and V(CO)6 forming the
equation (49). Hexacarbonylvanadium(0) has been found to -isocarbonyl compound VCp 2 (-OC)V(CO)5 containing
have a regular octahedral structure, and to be isostructural the linear VOCV arrangement.76
with the hexacarbonyls of group 6. The hexacarbonylniobate(I) and hexacarbonyltanta-
late(I) anions are well established. The [Nb(CO)6 ] anion
red./CO can be prepared at atmospheric pressure of CO from NbCl5 by
VCl3 [V(CO)6 ] (48) using a prereduction step with alkali metal/naphthalene at low
[cot]
temperature, followed by carbonylation of the intermediate
[V(CO)6 ] + H+ 1
H + V(CO)6 (49)
2 2 at low temperature in DME as solvent.77 Another method
of preparation,78 also operating at atmospheric pressure
The hexacarbonylvanadate(I) anion is prepared at room of CO, uses the reduction of NbCl5 with Mg/Zn/pyridine
temperature and atmospheric pressure by reducing VCl3 at room temperature and gives yields as high as 48%
with sodium in THF in the presence of catalytic amounts of recrystallized Na(THF)[Nb(CO)6 ]. The alkali metal
of cyclooctatetraene (cot); the actual reducing agent is derivatives of [M(CO)6 ] , M = Nb, Ta, are rapidly oxidized
presumably the cot2 di-anion.70 The reaction of equation (49) by air; the PPN derivatives are stable in air for short periods
is carried out with dry HCl in a hydrocarbon solvent. of time. PPN[Nb(CO)6 ] and PPN[Ta(CO)6 ] are isostructural;
Hexacarbonylvanadium(0) is black green in the solid state the hexacarbonyl anions possess an almost exact octahedral
and shows the expected magnetic behavior for a d5 , low- geometry with the following MC bond distances: NbCO,
spin complex from room temperature to 66 K, in which the 2.089 A; TaCO, 2.083 A.
2
T2g electronic ground state is coupled to vibrational modes. The oxidation of [Nb(CO)6 ] and [Ta(CO)6 ] by several
Below 66 K down to liquid helium temperature, the magnetic halide-containing oxidants (HX, CuX, CuX2 , AgX, FeX3 )
CARBONYL COMPLEXES OF THE TRANSITION METALS 13
results in a two-electron transfer (see equation 50) leading Studies on carbonyl derivatives of palladium(II), plat-
to the halide-bridged dimers of niobium(I) or tantalum(I). inum(II), silver(I), and gold(I) have established the following
With silver(I) salts containing the poorly coordinating anions points:
NO2 or BF4 , formation of the tertiary phosphine substituted
neutral hexanuclear clusters (equation 51) is observed.79 1. The halocarbonyl derivatives Pd2 X4 (CO)2 , Pt2 X4 (CO)2 ,
Bonding considerations on some of these systems have been PtX2 (CO)2 , and AuX(CO) are characterized by carbonyl
presented.80,81 stretching vibrations at high frequencies, sometimes
higher than CO itself (CO = 2143 cm1 ) (see Table 5)
2[M(CO)6 ] + 3X [M2 X3 (CO)8 ] + 4e (50) with values of CO usually decreasing in the sequence
M = Nb, Ta; X = Cl, Br, I
Cl > Br > I.
2. The tendency to form the halocarbonyls as a function
3NR4 [M(CO)4 (dmpe)] + 3AgX Ag3 M3 (CO)12 (dmpe)3 + 3NR4 X
of the halide decreases in the sequence Cl > Br > I.
(51) The carbonyl bromides of palladium(II), Pd2 Br4 (CO)2 ,
M = Nb, Ta; X = NO2 , BF4 and gold, AuBr(CO), tend to decarbonylate in the solid
state even under CO at atmospheric pressure, and the
The hexacarbonylmetalates(II) of group 4 can be corresponding carbonyl iodides are unknown.
synthesized by reducing the tetrachlorides with potassium 3. The values of the carbon platinum coupling constants
in the presence of a cryptand. In the case of hafnium, the JPt C decrease along the sequence Cl > Br > I, which
starting material is a tertiary-phosphine-carbonyl complex may be explained by a corresponding decrease of the
of the zerovalent metal (see equations 52 and 53). The PtCO -bond strength in the same sequence.
cryptand/(metal cation) system, characterized by a large mass
The available data suggest a small -contribution to the
and a low charge density, presumably has a stabilizing effect
M CO bond in these systems.
on the carbonyl anion. Reactions of equations (52) and (53)
The PdII CO bond strength has been estimated to be
are carried out with CO at atmospheric pressure.16
100 kJ mol1 , which is consistent with the values expected
for a 4d element in the +II oxidation state on the basis of
K/C10 H8 /CO
MCl4 (ether)n [K(15-crown-5)]2 [M(CO)6 ] (52) known thermochemical data for binary carbonyls of metals
15-crown-5
belonging to Groups 6 10 (see Section 8). In the absence of
M = Ti, Zr; ether = THF, n = 2; ether = DME, n = 1 a significant back-bonding contribution, the strength of the
K/C10 H8 /CO MCO bond would not increase by decreasing the oxidation
M(CO)4 (trmpe) [K(cryptand)]2 [M(CO)6 ] (53) state. This prediction would therefore justify the observation
cryptand 2.2.2
that Pd(CO)4 and Pt(CO)4 have not been observed as stable
M = Ti, Zr, Hf
species.
A predominant -contribution in MCO bonds can
generate a charge polarization within the MCO bond such
that the carbonyl carbon can become a site of nucleophilic
7 METAL CARBONYLS OF THE LATE attack. It has been pointed out89 that metal carbonyls with
TRANSITION ELEMENTS force constants higher than 17.2 mdyn A1 , as estimated from
the IR-active carbonyl stretching vibrations, should react
The only neutral binary metal carbonyl of groups with amines to give carbamoyl derivatives. Accordingly,
10 12 is Ni(CO)4 . Some cationic-carbonyl derivatives of
copper(I) and silver(I) have been detected in small equilibrium
concentrations in strongly acidic aqueous solution. The Table 5 Carbonyl stretching vibrations (IR) of halocar-
bonyls of palladium, platinum, and gold2,84
formulas of these species, deduced from spectroscopic
data,8285 are M(CO)n + (M = Cu, Ag). The instability of Compound CO (cm1 ) Solvent
Pd(CO)4 and Pt(CO)4 with respect to their decomposition to
the metal (see equation 54) suggests that the strength of the cis-Pd2 Cl4 (CO)2 a 2160 Toluene
trans-Pd2 Br4 (CO)2 2148 Toluene
MCO bond is not sufficiently high to counterbalance the trans-Pt2 Cl4 (CO)2 a 2119 Toluene
negative enthalpy change corresponding to the formation of 2122 Heptane
the metal from M(CO)4 and the positive entropy change due cis-PtCl2 (CO)2 2167, 2120 Heptane
to CO evolution. The enthalpy change for the vaporization cis-PtBr2 (CO)2 2156, 2115 Heptane
of nickel (430 kJ mol1 ) is higher than that of palladium trans-PtBr2 (CO)2 2136 Heptane
trans-PtI2 (CO)2 2122 Heptane
(381 kJ mol1 ),8688 thus suggesting that PdCO bonds are AuCl(CO) 2163 SOCl2
particularly weak. AuBr(CO) 2153 sym-C2 H4 Br2
cis-PtCl2 (CO)2 , with CO force constants of 19.01 and Table 6 Mean bond dissociation enthalpies (BDE) and
18.3 mdyn A1 , reacts with secondary amines to give the calculated first ligand dissociation energies (FDE) of some
binary metal carbonyls
carbamoyl derivatives shown in equation (5).
Although the formation of AgCO bonds in solu- Compound BDE (kJ mol1 )94,95 FDE (kJ mol1 )97
tion had been established in several systems,8285 iso-
lation and structural determination of products contain- Cr(CO)6 107 1 147
ing AgCO bonds are recent acquisitions.3,90,91 The car- Mn(CO)6 + 92
V(CO)6 171
bonyl derivatives of silver, Ag(CO)(OTeF5 )2 B(OTeF5 )2 , and Mo(CO)6 152 1 119
[Ag(CO)2 ][B(OTeF5 )4 ] have been crystallographically estab- W(CO)6 178 1 142
lished. In the former compound,90 silver is coordinated to Fe(CO)5 118 2
carbon monoxide and to two oxygen atoms of the boron- Ni(CO)4 147 106
containing ligand; the [Ag(CO)2 ]+ cation is constituted91 Pd(CO)4 27
Pt(CO)4 38
by two-coordinated linear silver(I), whose unique IR car-
bonyl stretching vibration is observed at 2198 cm1 . The
[Pt(CO)4 ]2+ cation, isolated as the [Pt(SO3 F)6 ]2 derivative,92
obtain these data or related ones, and pertinent review arti-
has an IR carbonyl stretching band at 2235 cm1 .
cles on the subject have appeared (see Bonding Energetics
of Organometallic Compounds).9497 A different approach to
this problem is the evaluation of enthalpy terms according
to second-law methods, by measuring equilibrium constants
8 METALCO BOND DISSOCIATION ENTHALPY as a function of temperature. This method has been par-
(BDE) ticularly useful for estimating thermodynamic parameters in
metal carbonyl cluster chemistry (see Section 2.5).
The thermodynamic stability of metal carbonyls has Heats of atomization of metals have well-known trends
attracted the interest of scientists for several decades.93 The within typical groups of transition elements (groups 6 9),86,87
understanding of the nature of the MCO bond should account that is, they increase down a group from the lighter to
for important observations, such as the isolation of stable the heavier element. By using a combination of several
metal carbonyls for metals in a wide range of oxidation experimental techniques, two main conclusions concerning
states, +IV to IV, the latter being encountered in the highly neutral metal carbonyls have been reached: (a) the MCO
reduced carbonyl metalates. Reliable MCO bond energies bond enthalpy contribution increases95 as the heat of
are essential in order to understand the behavior of these atomization increases down a group (typical sequences:
compounds, including their reactivity. For simplicity, mainly Cr Mo W; Fe Ru Os; Co Rh Ir); (b) the MCO bond
binary neutral metal carbonyls will be considered here, but enthalpy is normally greater than the metal metal bond
the general considerations on this problem usually apply to enthalpy estimated from the heat of atomization. Table 6
substituted metal carbonyls as well and to compounds in reports the MCOt (COt , terminal CO) mean bond enthalpies
oxidation states higher or lower than zero. For a neutral binary for some of the common binary metal carbonyls and the
metal carbonyl and its formation from the corresponding calculated97 first ligand dissociation energies. Within the
metal, vaporization of the metal and its reaction with CO to neutral compounds with the same electronic configuration, the
form the final product (equations 55a and 55b) are the relevant 4d compound generally has the lowest dissociation energy.
steps to be considered. The enthalpy and entropy contributions Point (b) is particularly relevant for systems such as
to the free-energy change of the process can be evaluated. Co2 (CO)8 , which exists in solution in an almost 1:1 ratio
between the carbonyl-bridged form and the nonbridged form
M(s) M(g) (55a) (see equation 25), and Mn2 (CO)10 , which is stable only in the
M(g) + nCO(g) M(CO)(g) (55b) nonbridged form both in solution and in the solid state. Single
metal metal bonds are not particularly strong for 3d systems;
As far as equation (55a) is concerned, the enthalpy term is this may explain the experimental observation that V(CO)6
accurately known for most metals,86,87 corresponding to the is mononuclear, since intraligand repulsion in the dinuclear
transfer of the solid metal to its state of a monoatomic gas species would not be compensated by a sufficiently strong
in its high-spin ground-state configuration. Equation (55b) vanadium vanadium bond.
contains the negative value of the bond enthalpy, which,
divided by the number of MCO bonds in the molecule,
gives the mean bond dissociation enthalpy. M(CO)n (g) differs
from M(CO)n (s) or M(CO)n (l) by the heats of sublimation or 9 REACTION MECHANISMS
vaporization, respectively.
Several experimental techniques, including thermochem- In metal carbonyl chemistry, two types of reactions have
istry and some spectroscopic methods, have been used to been studied from a mechanistic viewpoint: (a) substitution
CARBONYL COMPLEXES OF THE TRANSITION METALS 15
reactions, where no change of oxidation state is involved, reactivity usually observed has theoretical support. This result
and (b) redox reactions (see Mechanisms of Reaction of is important for catalysis.
Organometallic Complexes). Substitutions (see equation 56) A special case of substitution reaction is the migratory
have been extensively studied, while a relatively smaller insertion (see Migratory Insertion) reaction of alkyl or aryl
number of papers have appeared on electron-transfer reactions. metal carbonyls (see equation 58), by which an alkyl or
aryl metal carbonyl is converted into an acyl or aroyl metal
M(CO)n + L M(CO)n1 L + CO (56) carbonyl by the action of a Lewis base. This reaction has been
studied extensively, and in the case of Mn(Me)(CO)5 is found
For polynuclear metal carbonyls, similar processes have to proceed through a coordinatively unsaturated tetracarbonyl
been studied to a great extent, especially for the decacarbonyls resulting from methyl migration on to one of the terminal CO
of group 7, M2 (CO)10 (M = Mn, Re). A simple case groups in a cis position, (see equation 59).101
of substitution is the isotopic exchange reaction, for
which the enthalpy is substantially zero. The specific rate MR(CO)n + L M(COR)(CO)n1 L (58)
constants (or half-lives)98 for such exchange reactions, L = Lewis base
under exclusion of light, of some selected metal carbonyls k1 +CO, k2
are in Table 7. Slowly reacting species [Fe(CO)5 , d8 MnMe(CO)5
k1
Mn(COMe)(CO)4
CO, k2
Mn(COMe)(CO)5
configuration; Cr(CO)6 , Mo(CO)6 , W(CO)6 , d6 low-spin],
(59)
moderately reactive [V(CO)6 , low-spin d5 , possibly subject
to Jahn Teller (see Jahn Teller Effect) distortion], and
fast reacting species [Ni(CO)4 , d10 configuration] can be In the migratory insertion reaction, the central metal
recognized. The low reactivity of the hexacarbonyls of group atom does not alter its oxidation state, and a new car-
6 is consistent with the well-established observation that d6 , bon carbon bond is formed. As such, this reaction is
low-spin systems are substitutionally inert, independent of believed to constitute a fundamental step in several car-
oxidation state. Substitution reactions frequently occur by bon carbon forming catalytic processes (hydroformylation
a dissociative mechanism with a coordinatively unsaturated (see Hydroformylation), homologation (see Homologation
species being formally present in the rate-determining step Reactions), carbonylation of methanol to acetic acid, alkene
(see equation 57). polymerization). Migratory insertions can be catalyzed
by oxidizing agents102 or Lewis acids under homoge-
k1 neous or heterogenous conditions. In both cases, the
M(CO)n M(CO)n1 + CO (57) electrophilic character of the carbonyl carbon is further
k1
enhanced, thus making this an even more favorable site
Within compounds containing metals belonging to the same of intramolecular attack by the alkyl group, as shown
vertical sequence, that is, normally isostructural compounds in (7).
with the same number of valence electrons for the central metal
atom (for example, the hexacarbonyls of group 6), the order of
+
reactivity is often 3d < 4d > 5d,99 with the exception of the M C O
cyclopentadienyl derivatives of group 5, MCp(CO)4 (M = V, Me
Nb, Ta), for which the order of reactivity is V > Nb > Ta.100 (7)
Relevant to these findings are the data provided in Table 6
showing that the calculated97 first CO dissociation energy for
the hexacarbonyls and the tetracarbonyls is lowest for the 4d For metal carbonyls, redox reactions (see Redox Properties
term. Thus, at least for dissociative mechanisms, the order of & Processes) have been studied in a smaller number of cases,
relative to substitution reactions. The simplicity of binary
metal carbonyls and the possibility for these compounds to
Table 7 Rate of CO exchange with some binary
metal carbonyls98 undergo electron transfers make them excellent substrates for
studying redox processes in nonaqueous media. Convenient
Rate organometallic one-electron oxidants or reductants (number
of valence electrons in parenthesis) are103,104 V(CO)6
Compound t ( C) k (s1 ) 1/2
(17)/[V(CO)6 ] (18); [FeCp2 ]+ (17)/FeCp2 (18); V(6 -
Ni(CO)4 0 7.8 104 arene)2 (17)/[V(6 -arene)2 ]+ (16); VCp2 (15)/[VCp2 L2 ]+
Fe(CO)5 25 4y (18); CoCp2 (19)/[CoCp2 ]+ (18). These systems have the
Cr(CO)6 117 2.0 105 advantage that the uncharged species is soluble in organic
Mo(CO)6 116 7.5 105 solvents, including aromatic or aliphatic hydrocarbons. Most
W(CO)6 142 2.6 106
V(CO)6 10 7h common binary metal carbonyls, with the exception of
V(CO)6 , have redox couples complicated by the formation
16 CARBONYL COMPLEXES OF THE TRANSITION METALS
of metal metal bonded dimers in the oxidized form (see 9. M. Finze, E. Bernhardt, A. Terheiden, M. Berkei, H. Willner,
equations 60 63). D. Christen, H. Oberhammer, and F. Aubke, J. Am. Chem.
Soc., 2002, 124, 15385.
[Mn(CO)5 ] 1
2
Mn2 (CO)10 + e (60) 10. L. Andrews, T. J. Tague, G. P. Kushto, and R. D. Davy, Inorg.
[Re(CO)5 ] 1
Re2 (CO)10 +e
(61) Chem., 1995, 34, 2952.
2
11. M. Zhou, Q. Xu, Z.-X. Wang, and P. von Rague Schleyer, J.
[Co(CO)4 ] 1
2
Co2 (CO)8 +e (62)
Am. Chem. Soc., 2002, 124, 14854, references therein.
[V(CO)6 ] V(CO)6 + e (63)
12. P. J. F. de Rege, J. A. Gladysz, and I. T. Horvath, Science,
1997, 276, 776.
Evidence for a single-event, two-electron transfer process
13. K. Weissermel and H. J. Arpe, Industrial Organic Chemistry,
has been gathered in the reaction between the two d6 systems,
Verlag Chemie, Weinheim, 1978.
[Re(CO)5 ] and [Mn(CO)6 ]+ (see equation 64), followed by
redistribution (equation 65).105 14. For positive oxidation states, see: H. Willner and F. Aubke,
Organometallics, 2003, 22, 3612.
[Re(CO)5 ] + [Mn(CO)6 ]+ [Re(CO)6 ]+ + [Mn(CO)5 ] (64) 15. J. E. Ellis, Adv. Organomet. Chem., 1990, 31, 1.
+
[Re(CO)6 ] + [Mn(CO)5 ] Re2 (CO)10 + Mn2 (CO)10 16. J. E. Ellis, Organometallics, 2003, 22, 3322.
+ MnRe(CO)10 (65) 17. K. M. Chi, S. R. Frerichs, S. B. Philson, and J. E. Ellis,
Angew. Chem., Int. Ed. Engl., 1987, 26, 1190.
18. K. M. Chi, S. R. Frerichs, S. B. Philson, and J. E. Ellis, J. Am.
Chem. Soc., 1988, 110, 303.
10 RELATED ARTICLES 19. J. E. Ellis and K. M. Chi, J. Am. Chem. Soc., 1990, 112, 6022.
20. L. Mond, C. Langer, and F. Quincke, J. Chem. Soc. (London),
Bonding Energetics of Organometallic Compounds; 1890, 57, 749.
Cobalt: Organometallic Chemistry; Electron Transfer Reac-
tions: Theory; Electronic Structure of Organometallic Com- 21. E. Weiss, Angew. Chem., Int. Ed. Engl., 1993, 32, 1501.
pounds; Hydride Complexes of the Transition Metals; Iridium: 22. F. A. Cotton, Helv. Chim. Acta, Alfred Werner
Organometallic Chemistry; Iron: Organometallic Chemistry; Commemoration Volume, Verlag Helvetica Chimica Acta,
Manganese: Organometallic Chemistry; Mechanisms of Reac- 1967, 117.
tion of Organometallic Complexes; Palladium: Organometal- 23. F. Calderazzo, R. Ercoli, and G. Natta, in Organic Syntheses
lic Chemistry; Periodic Table: Trends in the Properties of via Metal Carbonyls, eds. I. Wender, and P. Pino, John Wiley
the Elements; Transition Metal Carbonyls: Infrared Spectra; & Sons, New York, 1968, and references therein.
Vanadium: Organometallic Chemistry. 24. F. A. Cotton, Prog. Inorg. Chem., 1976, 21, 1.
25. G. Brauer, Handbuch der Praparativen Anorganischen
Chemie, Dritter Band, Enke Verlag, Stuttgart, 1981;
W. Hieber, Adv. Organomet. Chem., 8, 1970, 1.
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CARBONYL COMPLEXES OF THE TRANSITION METALS 17
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18 CARBONYL COMPLEXES OF THE TRANSITION METALS
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Carbonylation Processes most of carbonylation chemistry is homogeneous, principally
because homogeneous catalysts generally give higher rates
by Homogeneous Catalysis and selectivities than heterogeneous systems (see Supported
Organotransition Metal Compounds). Numerous reviews
and books have appeared on this subject, particularly with
M. L. Parr respect to the industrially important area of Hydroformylation
Trinity College, Hartford, CT, USA catalysis. Some of the major books and reviews used
in preparing this chapter are listed here. Falbes book
Based in part on the article Carbonylation Processes by Homogeneous on New Syntheses with Carbon Monoxide contains the
Catalysis by George G. Stanley which appeared in the Encyclopedia most extensive compilation of references (almost 2000) on
of Inorganic Chemistry, First Edition.
hydroformylation and several other important CO catalysis
reactions up through 1978 79.1 A comprehensive 15-
1 Introduction 1 year review of hydroformylation and carbonylation was
2 Aldehydes and Alcohols Hydroformylation 2 published by Cornils et al. in 1995.2 The material presented
3 Carboxylic Acids, Esters, and Acyl Halides 19 in this excellent review will not be explicitly discussed
4 Ketones 27 here. A thorough review of both academic and industrial
5 Lactones and Lactams 28 developments in hydroformylation appears in Rhodium
6 Related Articles 31 Catalyzed Hydroformylation, edited by van Leeuwen and
7 References 31 Claver, published in 2000.3 Asymmetric carbonylation
reactions are discussed by Nozaki and Ojima in the second
edition of Catalytic Asymmetric Synthesis, published in 2000.4
The second edition of Applied Homogeneous Catalysis with
Abbreviations Organometallic Compounds, edited by Cornils and Herrmann,
was published in 2002.5 Chapter 2 deals specifically with
bar = 1 105 Pa 1 atmosphere of pressure; psig =
carbonylation and hydroformylation reactions and the reader
pounds/square inch gauge pressure (14.70 psig = 1 bar).
is referred to this comprehensive survey for a summary of
important advances in these areas. For the past several years,
Ungvary has written an annual survey covering advances in
the field of hydroformylation. The most recent of these reviews
(2004) is cited here.6
1 INTRODUCTION Most of the palladium chemistry mentioned was found
in Hecks7 classic work Palladium Reagents in Organic
Homogeneous carbonylation catalysis involves the tran- Synthesis. Industrial perspectives came from interviews
sition metal assisted addition of carbon monoxide (CO) with industrial chemists and the Encyclopedia of Chemical
to organic compounds to produce higher molecular weight Processing and Design, specifically the sections on Oxo
carbonyl-containing products. Carbonylation chemistry was Process Alcohols and Butyraldehydes and Butyl Alcohols.8
pioneered by Roelen (Ruhrchemie) and Reppe (IG Far- If a reaction or result in this review is not referenced it came
ben/Badische Anilin und Soda Fabrik (BASF)) in the late from one of the books mentioned here.1,3,7,8
1930s. Since then, it has developed into the highest volume and There was no possibility of even briefly mentioning all the
most important of the industrial homogeneous catalytic pro- known catalytic-carbonylation reactions in this chapter it is
cesses. The first 27 years of carbonylation catalysis involved that huge an area of catalysis. Instead, an industrial orientation
the use of simple metal carbonyl catalysts, high-reaction has been taken with topics covered more or less in order of
temperatures and pressures, and low-product selectivities. their commercial, then academic, significance. About half of
The situation changed in the mid-1960s with Wilkinson this review covers hydroformylation catalysis, which is the
and Hecks independent discoveries that organophosphine- largest homogeneous process carried out in industry today.
substituted rhodium and palladium complexes, respectively, An attempt has been made to present a balanced mixture of
were active catalysts for carbonylation reactions under milder the older classic work, new work, and some interpretations
reaction conditions. Since then, significant advances in catalyst based on current knowledge. This review will not cover
design have led to dramatic enhancements in both the rate and stoichiometric carbonylation reactions (see Organic Synthesis
regioselectivity of carbonylation catalysts. A number of these using Transition Metal Carbonyl Complexes).
improvements have had significant industrial applications, The most significant advances in carbonylation catalysis in
while many more of them have made carbonylation catalysis a the next several years9 will undoubtedly occur in the area of
very viable laboratory method for organic functionalizations. novel ligand systems, new solvents, and asymmetric induction,
Carbonylation catalysis encompasses a large and important which will be briefly covered here (see Asymmetric Synthesis
area of chemistry. Unlike many other catalytic reactions, by Homogeneous Catalysis).
2 CARBONYLATION PROCESSES BY HOMOGENEOUS CATALYSIS
2 ALDEHYDES AND ALCOHOLSHYDRO- HCo(CO)4 as the active catalytic species (see Cobalt:
FORMYLATION Organometallic Chemistry). In 1960 and 1961, Heck
and Breslow10,11 proposed what is now accepted as the
Hydroformylation, also known as the oxo reaction, is general mechanism for cobalt-catalyzed hydroformylation
the largest homogeneous industrial process in the world, (Scheme 1). Dissociation of CO from HCo(CO)4 produces the
with over 8 billion kg of aldehydes and alcohols produced 16e coordinatively unsaturated (see Coordination & Organo-
each year. Hydroformylation involves the reaction of alkenes metallic Chemistry: Principles and Electronic Structure of
with H2 and CO to produce aldehyde products (equation 1). Organometallic Compounds) complex HCo(CO)3 to which
Hydroformylation was discovered by Otto Roelen in 1938 alkene can bind. Alkene Insertion into the CoH bond (see
during an investigation of the origin of oxygenated products Mechanisms of Reaction of Organometallic Complexes)
occurring in the cobalt-catalyzed Fischer Tropsch Process. produces either the linear or branched alkyl species (linear
Roelens observation that ethylene, H2 , and CO were alkyl is shown in Scheme 1). Coordination of CO and
converted into propanal and, at higher pressures, diethyl ketone subsequent alkyl migration produces the acyl intermediate.
marked the beginning of hydroformylation catalysis.
Loss of CO, followed by oxidative addition of H2 to the
O H cobalt center produces the dihydride species (see Hydride
O
H2, CO Complexes of the Transition Metals). Reductive Elimination
R Rh or Co
+ of aldehyde and coordination of CO regenerates the starting
H R R (1)
catalyst HCo(CO)4 catalyst. This same general sequence of steps is
Linear Branched
the foundation for the proposed mechanisms of most other
Aldehydes
hydroformylation catalysts.
Cobalt catalysts completely dominated industrial hydro- An alternate bimetallic pathway was also suggested,
formylation until the early 1970s, when rhodium catalysts were but not favored, by Heck and Breslow (also shown in
commercialized. Most aldehydes produced are hydrogenated Scheme 1). The acyl intermediate could react with HCo(CO)4
to alcohols or oxidized to carboxylic acids. Esterification of to undergo intermolecular hydride transfer, followed by
the alcohols with phthalic anhydride produces dialkyl phtha- reductive elimination of aldehyde to produce the CoCo
late plasticizers that are primarily used for polyvinyl chloride bonded dimer Co2 (CO)8 . A common starting material for
plastics the largest single end-use. Detergents and surfac- HCo(CO)4 -catalyzed hydroformylation, Co2 (CO)8 is well-
tants make up the next largest category, followed by solvents, known to react with H2 under catalysis reaction conditions
lubricants, and chemical intermediates. to form two equivalents of HCo(CO)4 . The bimetallic
hydride transfer mechanism is operational for stoichiometric
hydroformylation with HCo(CO)4 and has been proposed to be
2.1 HCo(CO)4 Catalyst
a possibility for slower catalytic hydroformylation reactions
Roelens original research into hydroformylation involved with internal alkenes.12 The monometallic pathway involving
the use of cobalt salts that, under H2 /CO pressure, produced reaction of the acyl intermediate with H2 , however, has been
CO
Co2(CO)8 OC CO
+ H2
Co
+ CO O OC H
H R CO
Co2(CO)7 + Alkene
+ CO
H R
OC H
Co R OC CO
HCo(CO)4 OC Co
CO CO H
O OC
+ H2 + CO
CO
CO CO
OC CO OC CO
Co Co
OC R OC R
+ CO
O
Scheme 1
CARBONYLATION PROCESSES BY HOMOGENEOUS CATALYSIS 3
Indeed, the reaction conditions for HCo(CO)4 -catalyzed The extra steric bulk of HCo(CO)4 (compared to
hydroformylation are largely governed by the thermal HCo(CO)3 ) should favor addition of the alkene to give linear
instability of HCo(CO)4 , which produces metallic cobalt if alkyls. The lower probability of alkene reaction with the
the CO partial pressure is not kept high enough. As the saturated HCo(CO)4 catalyst is consistent with the reduced
reaction temperature is increased, the CO partial pressure activity at higher CO partial pressures. One can also explain all
required to maintain stability of HCo(CO)4 increases in a these features with the 16e HCo(CO)3 catalyst by proposing
logarithmic fashion (see Figure 1). Thus, the usual reaction that alkene isomerization is more facile with the resulting
temperatures needed to obtain a reasonable reaction rate 16e RCo(CO)3 species that results after reaction with alkene
(110 180 C) require rather high CO partial, and hence, total (Scheme 2).
H2 /CO pressures (200 300 bar). Under lower CO partial pressures a 16e RCo(CO)3
Increasing the CO partial pressure decreases the hydro- species will have a long enough lifetime to allow reverse
formylation reaction rate and the amount of alkene isomer- -Hydride Elimination (see Mechanisms of Reaction of
ization side reactions (see Hydrogenation & Isomerization Organometallic Complexes) and increase the possibility for
of Alkenes), while increasing the aldehyde linear to branched alkene reinsertion to the branched alkyl species, which is
product ratio. Pino proposed that the apparent marked differ- slightly more favored thermodynamically. At this point, CO
ence between HCo(CO)4 -catalyzed hydroformylation at low addition and insertion will yield a branched aldehyde, or
and high CO partial pressures was due to the existence of two another -hydride elimination can give alkene isomerization.
active catalyst species, HCo(CO)4 and HCo(CO)3 , formed This second mechanistic explanation is in line with more recent
from the CO association/dissociation equilibrium shown in results from Rh/PPh3 -catalyzed hydroformylation studies (see
Section 2.4).
The regioselectivity of HCo(CO)4 (or HCo(CO)3 ) for
1000
producing the more valuable linear aldehydes varies with
reaction conditions and alkene substrates used. With 1-alkenes
one can typically get linear to branched aldehyde ratios of 3 4
Stable to 1. There is a trade-off between rate and regioselectivity.
CO pressure (bar)
region
High CO partial pressure slows the rate of catalysis, but
100 increases the linear to branched aldehyde product ratio. Higher
CO partial pressures also lower alkene isomerization side
Unstable
reactions. Higher temperatures increase the reaction rate,
region but lower the linear aldehyde product regioselectivity and
increase various undesirable side reactions. Some aldehyde
10 Hydrogenation to alcohols is usually observed (5 12%),
100 150 200 250
although alkene hydrogenation is usually quite low (1%),
Temperature (C)
particularly under higher CO partial pressures. Aldehyde
hydrogenation is not generally considered to be a negative
Figure 1 Stability of HCo(CO)4 /Co2 (CO)8 species with respect to side reaction, since the aldehyde products are usually
precipitation of cobalt metal (cobalt concentration is 0.4 wt%) hydrogenated to alcohols in a subsequent reaction step.
4 CARBONYLATION PROCESSES BY HOMOGENEOUS CATALYSIS
R
OC
CO
Co
Alkene isomerization
OC H
OC CO R OC CO
Co OC CO Co
OC Co OC R
OC H
R Linear route
+ CO
OC CO
Co Branched aldehyde
OC
O
R
Scheme 2
commercial hydroformylation reactions. Although industrial reduction in the CO partial pressures required to stabilize
reactors are usually started with high-boiling solvents, after a the catalyst. Instead of 200 300 bar of H2 /CO pressure
while these heavy ends become the main solvent system for needed for HCo(CO)4 , the monophosphine-substituted cat-
the reaction. alyst HCo(CO)3 (PR3 ) only needed 50 100 bar pressure, and
One of the major problems in any large-scale industrial could be run at higher temperatures without any decomposition
homogeneous process, such as hydroformylation, is separation of catalyst to cobalt metal.
of the product from the catalyst at the end of the reaction. Another electronic effect is that the electron-donating
One advantage of HCo(CO)4 technology is that catalyst phosphine increases the hydridic nature of the hydride lig-
separation and recycling is well established. The two major and (HCo(CO)4 is quite acidic) and dramatically increases
methods of separating catalyst from product involve oxidation the hydrogenation capabilities of the HCo(CO)3 (PR3 ) cat-
of HCo(CO)4 to water-soluble CoII salts that are extracted alyst. This effect means that aldehydes produced from the
from the product stream, and flash evaporation of volatile initial hydroformylation are subsequently hydrogenated by
HCo(CO)4 from the high-boiling products. HCo(CO)3 (PR3 ) to produce alcohols as the final prod-
uct. Less electron-rich phosphines, such as PPh3 , give
less hydrogenation to the alcohol product, and lower
2.2 Cobalt Phosphine-modified Catalysts linear regioselectivities. The increased hydrogenation abil-
ity, however, also results in increased alkene hydrogenation
The first and only major variation on HCo(CO)4 hydro- that can range from 10 20% of the product distribution,
formylation catalysis involved research at Shell by Slaugh depending on the phosphine ligand used and the exact
and Mullineaux, in which the addition of trialkylphosphine reaction conditions. Because of the aldehyde hydrogena-
ligands (see Cobalt: Organometallic Chemistry and Phos- tion step, additional H2 is needed, so H2 /CO ratios of 2:1
phorus: Organophosphorus Chemistry) caused a dramatic (or slightly higher) are used. The proposed hydroformy-
change in the rate and regioselectivity.19 The electronic effect lation and hydrogenation mechanisms are both shown in
of substituting an electron-donating alkylated phosphine for Scheme 5.
one of the carbonyl ligands, to produce HCo(CO)3 (PR3 ), The final electronic effect of phosphine substitution is
results in stronger CoCO bonding. This causes a dramatic that the higher stability of the HCo(CO)3 (PR3 ) catalyst, due to
CO
OC PR3
Co
O CO CO
+ CO + H2
R
CO H
OC PR3 OC H
Co Hydrogenation Co
O H OC O R
R PR3
H CO CO
OC PR3 Alcohol
O Co
H R OC H
CO
+ Alkene R
H + CO
OC H OC PR3
Co Co
OC R
PR3 OC H
O
+ H2 + CO
Hydroformylation
CO
CO CO
OC PR3 OC PR3
Co + CO
Co
OC R OC R
O
Scheme 5
6 CARBONYLATION PROCESSES BY HOMOGENEOUS CATALYSIS
stronger CoCO bonding, means that this catalyst is less active Table 1 Hydroformylation of 2-pentene as a function of metal and
than HCo(CO)4 (about 5 10 times slower). Just as with the partial CO pressurea
unmodified cobalt catalyst, CO dissociation from the saturated
PCO (bar) Co2 (CO)8 Rh4 (CO)12
18e species is needed to open up an empty coordination site
on the cobalt to allow coordination of alkene and H2 . Higher- 45 12 12 26 25
reaction temperatures, therefore, are used in conjunction with 35 5 35 25 14 10
longer-reaction times and larger reactor volumes.
From a steric viewpoint, the considerably bulkier 100 13 7 48 16
trialkylphosphine ligand should, and does, favor formation of 48 6 26 7 28 1
linear products. While linear to branched ratios of only 2 3:1
a
are typically found for HCo(CO)4 , higher regioselectivities The percentage of aldehyde product formed at each site is indicated.
of 7 8:1 occur for HCo(CO)3 (PR3 ). There is a phosphine
Cone Angle cutoff at about 132 , after which the steric effects Perhaps not too unexpectedly, the linear to branched
of the phosphine ligand do not increase the product linear aldehyde regioselectivity of HRh(CO)4 is lower than that
regioselectivity any further. found for HCo(CO)4 , consistent with the larger size of a
Phosphine-modified cobalt hydroformylation is only used rhodium atom relative to cobalt. This results in less steric
commercially by Shell. It is tightly coupled to Shells Higher crowding about the rhodium center, leading to less steric
Olefins Process (SHOP, see Metathesis Polymerization differentiation for the alkene insertion step into the MH bond
Processes by Homogeneous Catalysis) that produces a to form a linear or branched alkyl group. With 1-pentene,
C4 through C20 mixture of linear, internal alkenes for HCo(CO)4 gives a linear to branched aldehyde ratio of 4:1
hydroformylation to detergent-grade alcohols. under optimum conditions, while HRh(CO)4 can only reach
a 1.6:1 ratio. As with HCo(CO)4 , HRh(CO)4 is an active
isomerization catalyst, but its lower regioselectivity leads to
2.3 HRh(CO)4 Catalyst more extensive distributions of the aldehyde products. The
isomerization ability is related to the partial CO pressure, with
In 1952, it was discovered by Schiller that rhodium salts considerably more isomerization occurring at lower partial CO
generated highly active hydroformylation catalysts. It was pressures. (Table 1 illustrates this for the hydroformylation of
from these early studies that rhodium was estimated to be 2-pentene from the work of Pino and coworkers.) As with
1000 to 10 000 times more active than cobalt. Rhodium HCo(CO)4 , this is explained by the formation of higher
was also found to be very selective to aldehydes, with little amounts of the 16e unsaturated HRh(CO)3 and its longer
hydrogenation to alcohols observed under normal catalysis lifetime under low CO partial pressures.
conditions. It was suggested early on that HRh(CO)4 was the HRh(CO)4 is used by Ruhrchemie in the hydroformylation
active catalyst species, analogous to HCo(CO)4 , and the same of certain branched alkenes that can only give a single product
monometallic mechanism was proposed (Scheme 6). due to the location of the branch that restricts both alkene
isomerization and product regioselectivity. In this special
case, the high activity of HRh(CO)4 is not off-set by poor
CO aldehyde regioselectivity.
OC CO
Rh Another similarity between HCo(CO)4 and HRh(CO)4 is
O
H
that they are only stable under certain reaction conditions.
OC Unlike HCo(CO)4 , HRh(CO)4 does not usually precipitate
H R CO
+ CO + Alkene out as metallic rhodium, but rather forms stable rhodium
R carbonyl clusters such as Rh4 (CO)12 and Rh6 (CO)16 . Indeed,
H
OC H just as Co2 (CO)8 is a common catalyst precursor for cobalt
Rh R OC CO
Rh hydroformylation, Rh4 (CO)12 is often used as a starting species
OC
CO H for rhodium hydroformylation.
O OC Unlike HCo(CO)4 and (acyl)Co(CO)4 species, which
+ H2 + CO are readily observed via FT-IR spectroscopy, the rhodium
CO monometallic analogs are more difficult to observe because
CO CO of their higher reactivity.20 The ready formation of easily
OC CO OC observable and isolable rhodium carbonyl clusters has led to
Rh CO
Rh
+ CO some conflicting reports on whether HRh(CO)4 is the true
OC R
OC R catalyst.
O
Garland has reported a detailed kinetic and mechanistic
study of the unmodified rhodium catalyst system using in situ
Scheme 6 FT-IR techniques and has concluded that the active catalyst
CARBONYLATION PROCESSES BY HOMOGENEOUS CATALYSIS 7
is indeed HRh(CO)4 , or more precisely, HRh(CO)3 .21 The Table 2 Rate constants and regioselectivities for the hydroformy-
rate-determining step in the catalytic cycle is hydrogenolysis lation of 1-hexene using Rh(acac)(CO)2 with different PPh3
concentrationsa
of the (acyl)Rh(CO)4 species, although the concentration of
HRh(CO)4 is dependent on cluster fragmentation/reformation [Rh] [PPh3 ] PPh3 /Rh kobs (min1 mM Linear:branched
equilibrium. In particular, Garlands kinetic data support (mM) (M) ratio Rh1 ) ratio
cluster fragmentation equilibria in the presence of alkenes
(equation 5). 0.5 0.41 820 0.032 11
1 0.82 820 0.016 17
Rh4 (CO)12 + 2CO
{Rh4 (CO)14 } + H2
4(acyl)Rh(CO)4 a
Reaction conditions: 90 psig, 1:1 H2 /CO, 90 C.
(5)
of 1-alkenes could be obtained under ambient conditions
2.4 Rhodium Phosphine Catalysts (25 C, 1 bar, 1:1 H2 /CO). At higher temperatures the rate
increased, but the regioselectivity dropped (9:1 at 50 C).
In 1965, Osborn, Young, and Wilkinson reported that Running under 80 100 bar of H2 /CO decreased the linear to
RhI PPh3 complexes were active and highly regioselective branched aldehyde selectivity to only 3:1.
hydroformylation catalysts for 1-alkenes, even at ambient con- Pruett (at Union Carbide) quickly provided the next
ditions. Although Slaugh and Mullineaux had filed a patent in critical discovery that, along with the work of Booth and
1961 that mentioned Rh/phosphine combinations for hydro- coworkers at Union Oil, allowed commercialization of the
formylation catalysis, it was Wilkinsons work that really HRh(CO)(PPh3 )2 technology. They found that the use of
ignited serious interest in rhodium phosphine hydroformyla- rhodium with excess phosphine ligand created an active,
tion catalysts. The initial catalyst system was derived from selective, and stable catalyst system at 80 100 psig and
Wilkinsons Catalyst, RhCl(PPh3 )3 , but it was rapidly discov- 90 C.22 Union Carbide, in conjunction with Davy Powergas
ered that halides were inhibitors for hydroformylation. It is and Johnson Matthey, subsequently developed the first
best, therefore, to start with rhodium precursor complexes that commercial hydroformylation process using rhodium and
do not contain halides. HRh(CO)(PPh3 )3 and Rh(acac)(CO)2 excess PPh3 . The need for excess phosphine arises from the
are two commonly used starting materials for hydroformy- facile RhPPh3 dissociation equilibrium shown in Scheme 8.
lation. The currently accepted core catalytic mechanism for Loss of PPh3 from HRh(CO)(PPh3 )2 generates considerably
Rh/PPh3 hydroformylation is shown in Scheme 7, and is more active, but less regioselective, hydroformylation
essentially a hybrid of Wilkinsons original associative and catalysts. The addition of excess phosphine ligand shifts the
dissociative mechanisms. The various steps are directly anal- phosphine dissociation equilibrium back towards the more
ogous to Hecks mechanism for HCo(CO)4 (see Scheme 1). selective HRh(CO)(PPh3 )2 catalyst. This explains why higher
Wilkinson noted that HRh(CO)(PPh3 )2 was very selective CO partial pressures lower the product regioselectivity, in
for the formation of aldehyde products (no alcohol formation, marked contrast to the observation made in the case of
no alkene hydrogenation or isomerization) and that very high HCo(CO)4 -catalyzed hydroformylation.
linear to branched aldehyde selectivities of 20:1 for a variety There has been considerable discussion on the exact nature
of the rhodium species that yields high product selectivity.
Wilkinson originally proposed that high regioselectivities
OC PPh3 resulted from alkene coordination to the bisphosphine species
Rh HRh(CO)2 (PPh3 )2 to generate a 20e six-coordinate complex.
O
OC H Alkene insertion into the RhH bond would then produce
H R
+ Alkene the 18e Rh(alkyl)(CO)2 (PPh3 )2 complex. This mechanism
is commonly referred to as Wilkinsons associative pathway.
H R
H PPh3 Since 20e species are generally not favored as intermediates in
Rh OC PPh3 organometallic mechanisms, the 16e species HRh(CO)(PPh3)2
R
Ph3P Rh
CO
has become the generally accepted selective catalyst (see
O Ph3P H Scheme 7).
The regioselectivity of HRh(CO)(PPh3 )2 is strongly related
+ H2
to the concentration of PPh3 in solution (up to a certain point)
and the H2 /CO ratio used. Commercial hydroformylation
OC PPh3 OC PPh3
reactions are run using solutions that have PPh3 concentrations
Rh Rh
Ph3P Ph3P of 0.3 M or higher. This corresponds to PPh3 weight
R + CO R percentages of 8 50% of the total solution in commercial
O
reactors. The effect of PPh3 concentration on the rate and
selectivity for the hydroformylation of 1-hexene can be seen
Scheme 7 in Table 2.
8 CARBONYLATION PROCESSES BY HOMOGENEOUS CATALYSIS
PPh3 PPh3 CO CO
Ph3P Rh H OC Rh H OC Rh H OC Rh H
PPh3 PPh3 PPh3 CO
Scheme 8
Note that doubling the PPh3 concentration cuts the rate alkyldiphenylphosphines or, in the worst case, phosphide-
constant in half, even though the rhodium concentration was bridged dimers which are inactive for hydroformylation
also doubled! The selectivity, on the other hand, increases (Scheme 9).
to 17:1 for the C7 aldehyde linear to branched ratio. The This fragmentation process has been studied and proceeds
ultimate experiment of running HRh(CO)(PPh3 )2 in molten by oxidative addition of the PPh bond to an unsaturated
PPh3 has been done with propylene, giving a 16:1 linear to Rh center.26,27 A separate PPh3 -activation process involving
branched aldehyde ratio. Commercially, propylene is run with Orthometalation of the phenyl group can also occur. Tri-
PPh3 concentrations around 0.4 M, which gives a linear to arylphosphine ligands and phosphite ligands are particularly
branched selectivity of 8 9:1. Lower CO partial pressures susceptible to this fragmentation because of the availability
also would be expected to favor higher regioselectivities, and of - or lone-pair electron density on the ligands that can
this is indeed the case. Rh/PPh3 reactions are often run with interact with an empty Rh orbital. The fact that they are
an excess of hydrogen (2:1 H2 /CO ratios are common). Too moderate to poor electron-donating ligands also enhances the
high a hydrogen partial pressure, or too low a CO partial electrophilicity of the rhodium center.28 Trialkylphosphine
pressure, however, will increase the alkene hydrogenation and ligands should be relatively inert to these types of Rh-induced
isomerization side reactions to an unacceptable level. fragmentations due to the lack of any -electron density on the
It was assumed early on, in analogy to the HCo(CO)4 cat- ligand. The considerably stronger -donation ability of alky-
alyst system, that the rate-determining step was H2 addition lated phosphines also works to decrease the electrophilicity
to the RhI acyl species. This assumption has been disputed of the rhodium center. Unfortunately, trialkylphosphine lig-
by several authors. Kastrup and coworkers concluded from ands generally lower both the rate and selectivity of rhodium
31 hydroformylation catalysts.
P NMR studies that the rate-determining step could be
the initial coordination of alkene to the HRh(CO)(PPh3 )2 The electronic and steric properties of the phosphine
catalyst species.23 Moser and coworkers, in a similar vein, ligand(s) can have dramatic effects on the rate and selectivity
proposed that the rate-determining step is CO dissociation of the rhodium catalysts. As mentioned above, electron-rich
from HRh(CO)2 (PPh3 )2 to once again generate the 16e alkylated phosphines generally have a negative effect on
species HRh(CO)(PPh3 )2 .24 Combining both of these pro- the rate and regioselectivity, while more electron deficient
posals, Unruh concluded that several of the fundamental phosphines such as PPh3 and phosphites (see Electron
steps in Rh/PPh3 hydroformylation appear to have similar Deficient Compound) generate more active and regioselective
rate constants, making it difficult to specify one overall rate- catalysts (Table 3).
determining step, as they may probably vary with the exact Some of the values in Table 3 are deceptive. The very low
reaction conditions. The complexity of the phosphine/CO activity of P(O-p-MeOC6 H4 )3 may well be caused by ligand
ligand dissociation/association processes and the many cat-
alytically active rhodium complexes present was most clearly
pointed out by Tolman and Faller, who presented a three- Ph Ph Ph
dimensional mechanistic scheme for the hydroformylation of Ph P
P Rh Rh
alkenes by Rh/PPh3 complexes.25 Scheme 7, in contrast, only P
Rh Rh
indicates the core catalytic cycle that is believed to give the Ph Ph
highest product aldehyde regioselectivity.
The other important reason for adding excess phosphine R Rh RO OR
RO
ligand is to minimize ligand fragmentation reactions that lead P
RO O
to catalyst deactivation. If a 14e highly unsaturated species P Rh Rh
P
such as HRh(CO)(PPh3 ) is formed, the very electrophilic
Rh RO OR
metal center can attack the PPh3 ligand (either intra- or
intermolecularly) (see Electrophilic Reaction). This leads
to cleavage of the PPh bond and formation of either Scheme 9
CARBONYLATION PROCESSES BY HOMOGENEOUS CATALYSIS 9
Table 3 Relative rates and regioselectivities for the hydroformy- alkyl or aryl substituents generally form very poor hydro-
lation of 1-octene using HRh(CO)(PR3 )2 catalysts with different formylation catalysts that give low rates and selectivities, as
phosphine ligandsa
well as extensive alkene isomerization and hydrogenation side
Cone Linear:branched reactions. However, several investigations have shown that
Phosphine angle ( ) Rel. rate ratio chelating phosphines with large bite angles (n 100 130 )
(see Bite Angle) can influence the activity and selectivity in
PPh3 145 7.7 4.6
P(OPh)3 128 5.4 6.1
rhodium-catalyzed hydroformylation reactions. van Leeuwen
P(O-o-MeC6 H4 )3 141 5.2 3.6 and coworkers have discovered that by increasing the bite
P(O-p-ClC6 H4 )3 128 4.9 13.3 angle of the bisphosphine ligand in complexes of the general
P(O-n-Bu)3 112 4.5 4.3 formula [RhL2 (CO)2 ] (L2 = bisphosphine), the steric bulk at
P(O-p-PhC6 H4 )3 128 3.9 5.7 the metal increases and this ultimately leads to the preferen-
P(O-o,o-Me2 C6 H3 )3 190 3.4 0.9
P(O-o-PhC6 H4 )3 152 2.8 1.1
tial formation of the linear aldehyde.30 Xantphos-type ligands
P(n-Bu)3 132 1.2 2.4 ((1), natural n 102 123 ) have been crucial in the study
P(O-p-MeOC6 H4 )3 128 1 4.9 of bite angle effects on the activity and selectivity of hydro-
formylation reactions. Ligands such as DPB-xantphos (2) and
a
Reaction conditions: 10:1 PR3 to Rh ratio, 80 100 psig, 90 C. POP-xantphos (3) have shown good activity for the selective
rhodium-catalyzed hydroformylation of internal alkenes to
fragmentation and catalyst deactivation. The low linear to linear aldehydes.
branched selectivity for the very bulky P(O-o,o-Me2 C6 H3 )3
ligand probably results from phosphite dissociation to form
small amounts of very active HRh(CO)4 that hydroformylates
with low regioselectivity. Under the proper conditions,
phosphite ligands produce extremely active rhodium catalysts
O
(see Section 2.7). Unfortunately, phosphite ligands are also the
most susceptible to rhodium-induced fragmentations. New O P P
developments in the exploration of catalytic intermediates
Ph2P PPh2
by in situ high pressure IR (HP-IR) techniques have been
reported by Kamer and coworkers.29 The hydroformylation of
1-alkenes with phosphite-supported rhodium complexes was (1) (2)
studied in situ with a rapid-scan IR technique. The predominant
species in this reaction was identified as RhC(O)R(CO)3 L(L =
2-tert-butyl-4-methylphenylphosphite). Labeling experiments Stereoselectivity in hydroformylation reactions, as a result
were carried out where it was possible to study the individual of the supporting ligand set (e.g. large bite angle diphosphines
elementary steps in the catalytic cycle. or chiral diphosphines) or by stereocontrol of the substrate has
Chelating phosphines (see Coordination & Organo- also been discussed by Breit.31 Rhodium complexes supported
metallic Chemistry: Principles) have interesting effects on by large bite angle diphosphines such as bisbi, biphephos and
hydroformylation. R2 P(CH2 )x PR2 (x = 2 4) ligands with xantphos, shown in Scheme 10, are now well-established
MeO OMe
t-Bu O O t-Bu
P P O
O
O O O
Scheme 10
10 CARBONYLATION PROCESSES BY HOMOGENEOUS CATALYSIS
O
H2/CO H2
OH OH OH
H HO
Allyl alcohol 1,4-Butanediol
Scheme 11
CARBONYLATION PROCESSES BY HOMOGENEOUS CATALYSIS 11
coordinated SnCl3 ligand. The tin is not needed for alkene Table 5 Hydroformylation of 1-octene with rhodium and plat-
insertion into the PtH bond, nor for CO insertion into the inum tin complexes supported by amine, arsine and phosphine
ligandsa
resulting alkyl to generate the acyl species. SnCl2 is needed,
however, for H2 addition to the Pt center and elimination Natural bite
of the product aldehyde. The first few steps in Scheme 13 angle, Linear:branched
could, therefore, be written without the SnCl3 ligand. The Metal/Ligand n b ( ) TOF ratio
role of the SnCl3 ligand is believed to be the removal of [Rh]/PP 110.1 240 50
electron density from the Pt center to help dissociate a CO [Rh]/NN 90 3.0
ligand from an 18e saturated five-coordinate species, such as [Rh]/AsAs 112.9 500 2.9
Pt(acyl)(Cl)(CO)(PPh3 )2 . This would open up a coordination [Rh]/AsP 111.4 84 8.9
site to allow H2 oxidative addition to the Pt center and [PtSn]/PP 18 230
[PtSn]/NN <1 1.9
subsequent elimination of aldehyde product. [PtSn]/AsAs 210 >250
[PtSn]/AsP 350 200
d(aldehyde)
= k[alkene][Pt]1.5 [H2 ][CO]0.5 (6)
dt a
Reaction conditions: 5:1 ligand to Rh, 20 bar, 1:1 CO/H2 , 80 C;
2:2:1 ligand:SnCl2 :Pt, 40 bar, 1:1 CO/H2 , 60 C. b Natural bite angle
Although the Pt/Sn/PPh3 catalyst system has been described for xantamine, xantarsine and xantphos ligands.
as highly active, this activity is relative to that of Pt catalysts
without SnCl2 , which are extremely slow. Hydroformylation
rates for Pt/Sn/PPh3 range from about 25 to 50 turnovers/h for
1-alkenes at 70 C and 1500 psi. This rate can be compared
to Rh/PPh3 , which produces 500 turnovers/h with 1-hexene
giving a linear to branched aldehyde product ratio of 17:1 at O
90 psig and 90 C. Ph2E EPh2
Interest in Pt/Sn hydroformylation arose from Stilles
E, E = P,P; N,N; As,As; N,P; As,P
asymmetric hydroformylation with chiral chelating phosphine
ligands that gave >96% enantiomeric excess (ee) for the (9)
branched aldehyde products of substrates such as vinyl
arenes and vinyl acetate (see Asymmetric Synthesis by parahydrogen-induced polarization (PHIP) in hydroformy-
Homogeneous Catalysis). Unfortunately, the very low rates, lation has been reported by Eisenberg and coworkers.42
poor branched to linear selectivities, and need for an aldehyde- Hydroformylation of 1-hexene in the presence of cis-
trapping agent limited the commercial appeal of this catalyst. [PtCl2 (CO)(PPh3 )]-SnCl2 using parahydrogen yields the
Note that this platinum catalyst uses an optically active- expected aldehyde product in which the aldehydic resonance
chelating phosphine, which implies that both phosphines can
exhibits net emission in the 1 H NMR spectrum. This is the
remain coordinated during the catalytic cycle, unlike that
first observation of a PHIP effect for a single-proton transfer
shown in Scheme 14.
process.
More recently, an excellent review of sulfur-containing
ligands in a variety of homogeneously catalyzed reactions,
including platinum tin hydroformylation, was published by 2.6 Polymetallic Catalysts
Claver and coworkers and so this area will not be discussed
here.40 The development of amine and arsine analogues of There have been numerous reports on dimer and cluster
xantphos-type ligands and their application in platinum tin catalysis for hydroformylation. Indeed, it was realized
catalyzed hydroformylation has been reported by van Leeuwen early on that cobalt and rhodium carbonyl dimers and
and coworkers.41 The amine-based ligands do not exhibit clusters were viable catalyst precursors for modified or
good activity probably due to the electron-donating capabil- unmodified hydroformylation catalysts. Muetterties proposed
ity of the diphenylamine group. The arsine-based systems, the cluster-surface analogy, which stated that molecular
however, show comparable activities to xantphos-supported metal clusters may be reasonable models of heterogeneous
systems due to the formation of [(ligand)Rh(CO)2 H] and metal surfaces in catalysis (see Polynuclear Organometallic
[(ligand)Rh(CO)2 ]2 complexes. In the case of PtSn catalyzed Cluster Complexes and Dinuclear Organometallic Cluster
hydroformylation of 1-octene under mild conditions, xantar- Complexes).43 It was recognized that on metal surfaces,
sine and the mixed phosphine arsine xantphosarsine ligands cooperativity between two or more metal centers in activating
(9) exhibit superior activity and selectivity compared to xant- substrates and in doing catalysis often played an important
phos. A comparison of results for platinum tin and rhodium- factor in the catalytic activity of heterogeneous catalysts.
catalyzed reactions with various ligands is shown in Table 5. This proposal ignited a worldwide effort by transition metal
Parahydrogen has been utilized as a mechanistic probe in dimer and cluster chemists to show that polymetallic systems
a number of reactions involving hydrogen. The application of could be effective homogeneous catalysts. Pittman and
CARBONYLATION PROCESSES BY HOMOGENEOUS CATALYSIS 13
H R OC SnCl3
Pt
Ph3P H
+ Alkene R
H
H SnCl3 OC SnCl3
Pt R Pt
Ph3P Ph3P H
CO
O
+ H2
OC SnCl3 OC SnCl3
Pt R Pt
Ph3P + CO Ph3P R
O
Scheme 14
coworkers reported that 1-pentene could be hydroformylated equivalent of HRh(CO)(PPh3 )2 caused an increase in the
by the intact cobalt clusters (10).44 catalytic activity of 90 150%. Addition of more than 0.3
equivalents, however, caused a decrease in the activity
relative to the starting HRh(CO)(PPh3 )2 catalyst. Di- and
R polyphosphine-bridged rhodium species, such as (11) and
C (12), were spectroscopically identified at about the same time.
OC
CO
OC Co CO P P
Co Co CO
OC CO
OC CO Rh Rh
Rh P P Rh
(10)
P P
(11) (12)
These clusters gave linear to branched aldehyde ratios of
between 1 and 5:1 (2.5 being typical) at temperatures of
90 150 C and pressures of 400 1100 psi. The highest linear This observation led to the proposal that tethering two
aldehyde regioselectivities were found, as with monometallic rhodium centers together via the bisphosphine ligands was
cobalt catalysts, at lower temperatures and higher pressures. producing some sort of bimetallic cooperativity between
The intact clusters could be isolated in near-quantitative the two metal centers. An intramolecular hydride transfer,
yields after the catalysis. One important piece of evidence analogous to the intermolecular hydride transfer proposed by
that fragmentation to HCo(CO)4 was not occurring was Heck (Scheme 1), enhanced by the proximity of the two metal
obtained from the influence of phosphine ligands on the centers, seemed a very likely possibility.
chemoselectivity of the catalysis. The addition of 2 4 Fragmentation has been a major and continuing problem
equivalents of PPh3 improved the stability of the cluster in polymetallic catalyst systems. Longoni and coworkers
(similar to the monometallic catalysts), but did not increase reported in 1984 that the Co2 Rh2 (CO)12 mixed-metal cluster
hydrogenation activity to produce alcohol products, quite was more active than either the parent Co4 (CO)12 or
unlike monometallic HCo(CO)3 (PR3 ) catalysts.45 Recent Rh4 (CO)12 cluster species.48 This higher activity was proposed
high-pressure IR studies of phosphine-substituted analogs of to be caused by heterobimetallic cooperativity between the Co
(7) show that there is no observable cluster fragmentation and Rh centers in the cluster. Garland, however, showed that
under catalytic conditions (150 C, 600 psi), even over the higher activity of the Co2 Rh2 (CO)12 mixed-metal cluster
extended periods of time (2 days).46 was simply due to the more facile fragmentation of this cluster
Sanger and coworkers reported an unusual effect of certain into reactive HRh(CO)4 monometallic catalyst species.49
bisphosphine ligands, Ph2 P(CH2 )n PPh2 , on the activity of Hidai and coworkers in the mid-1980s also observed a
HRh(CO)(PPh3 )2 hydroformylation catalysts.47 The addition cooperative mixed-metal effect for Co2 (CO)8 and Ru3 (CO)12
of 0.25 equivalents of Ph2 P(CH2 )n PPh2 (n = 2 4) per cluster mixtures.50 They observed a rather dramatic 27-fold
14 CARBONYLATION PROCESSES BY HOMOGENEOUS CATALYSIS
increase in the rate for the hydroformylation of cyclohexene transfer assisting in the elimination of aldehyde product. Ab
with a 9.9:1 Ru:Co ratio relative to Co2 (CO)8 alone. More initio molecular orbital studies have been performed on this
modest rate increases (3 times at an optimum Ru:Co ratio system, providing some support for the various mechanistic
of 1:1) were seen for the hydroformylation of 1-hexene. The steps.54
linear to branched aldehyde product ratio, however, was the There are, however, a number of experimental obser-
same as for Co2 (CO)8 . Discrete Co/Ru clusters, however, vations on this bimetallic catalyst that could indicate that
were not proposed. Hidai suggested instead that the clusters fragmentation to generate monometallic catalyst species
fragmented, and that the Heck bimetallic intermolecular is occurring. Foremost is that the selectivity of Rh2 (-
hydride transfer mechanism (see Scheme 1) was responsible SR)2 (CO)2 (PR3 )2 is essentially the same as that seen for
for the rate increases. [HRu(CO)4 ] has been shown to react monometallic Rh/PPh3 catalysts. Furthermore, the effect
much more readily with (acyl)Co(CO)4 to eliminate aldehyde on rate and regioselectivity of adding excess PPh3 to the
than HCo(CO)4 , probably because it is more nucleophilic.51 bimetallic catalyst almost exactly parallels the monometal-
Ru is also believed to activate H2 more readily than cobalt. lic rhodium catalyst. There is a catalytic induction period
Thus, it was proposed that the Ru/Co cooperativity was in for Rh2 (-SR)2 (CO)2 (PR3 )2 that would be consistent with
the form of an intermolecular hydride transfer to facilitate the the need to wait for fragmentation to generate monometal-
elimination of aldehyde product. lic complexes. Kalck has observed that when the two
One cluster system that has given very high product dimer complexes Rh2 (-pz)2 (CO)2 (PR3 )2 (pz = pyrazolate)
regioselectivities is [HRu3 (CO)11 ] , reported by Suss Fink and Rh2 (-SR)2 (CO)2 (PR3 )2 are mixed together, the mixed-
and coworkers.52 This cluster catalyst has linear to bridge bimetallic complex cis-Rh2 (-pz)(-SR)(CO)2 (PR3 )2
branched aldehyde regioselectivities of up to 70:1 for the is slowly produced. This observation implies that some sort of
hydroformylation of propylene. The very high selectivity, dissociative/reassociative equilibrium process may be taking
coupled with the fact that monometallic Ru hydroformylation place.
catalysts do not have high product regioselectivities, strongly Another bimetallic rhodium complex that may provide
points to the presence of intact clusters performing the an indisputable example of bimetallic cooperativity in
catalysis. One can then ask whether the hydroformylation hydroformylation catalysis has been reported by Stanley
is occurring only on a single-metal center, or whether and coworkers.55 They designed a novel binucleating
one is having bi- or polymetallic cooperativity in the tetraphosphine ligand (et,ph-P4; (13r), (13m)) that can
catalysis. Suss Fink has discussed the possibility of bimetallic both bridge and chelate two transition metal centers,
cooperativity, but strong evidence either way has not been producing bimetallic complexes that only have a single, very
found. Unfortunately, the activity of this cluster catalyst is conformationally flexible bridging group.
extremely low (e.g. only 50 turnovers over the course of 66 h
at 10 bar H2 /CO/propylene and 70 C in diglyme), limiting its Ph PEt2 Et2P PEt2
practical appeal. P P P P
A bimetallic hydroformylation catalyst that has attracted Ph Ph Ph
interest is the thiolate-bridged rhodium complex Rh2 (- Et2P
SR)2 (CO)2 (PR3 )2 studied by Kalck.53 This complex is a racemic-et,ph-P4 meso-et,ph-P4
rather active hydroformylation catalyst for 1-alkenes, giving (13r) (13m)
rates that are faster than HRh(CO)(PPh3 )2 . (Kalck has
claimed that Rh2 (-SR)2 (CO)2 (PR3 )2 is four times faster It was found that [racemic-Rh2 (nbd)2 (et,ph-P4)](BF4 )2
than HRh(CO)(PPh3 )2 , but no excess PPh3 was used for (nbd = norbornadiene) was a catalyst precursor to a highly
HRh(CO)(PPh3 )2 ; this probably leads to deactivation of active and regioselective hydroformylation catalyst for 1-
the monometallic catalyst by PPh3 fragmentation.) Reaction alkenes under mild conditions. The bimetallic catalyst gave
conditions are typically mild for a Rh-based catalyst: 5 bar hydroformylation rates for 1-hexene that were 40% faster
1:1 H2 /CO and 80 C. IR and 31 P NMR studies of the than the Rh/PPh3 monometallic catalyst, and a linear to
catalyst under hydroformylation conditions only show the branched aldehyde regioselectivity of 28:1, relative to 17:1
presence of Rh2 (-SR)2 (CO)2 (PR3 )2 or Rh2 (-SR)2 (CO)4 . for HRh(CO)(PPh3 )2 with 0.82 M PPh3 (conditions: 90 C,
Some excess PPh3 is needed to keep the bimetallic catalyst 90 psig 1:1 H2 /CO). Since neither the rac-Rh2 (nbd)2 (et,ph-
in the Rh2 (-SR)2 (CO)2 (PR3 )2 state, since the tetracarbonyl- P4)2+ precursor complex, nor the proposed active catalyst
substituted bimetallic species Rh2 (-SR)2 (CO)4 is inactive for species rac-Rh2 H2 (CO)2 (et,ph-P4), have a RhRh bond it
hydroformylation under mild conditions. The apparent high was fairly straightforward to prepare mono- and bimetallic
activity of this bimetallic catalyst, coupled with the lack of model systems to test whether the two metal centers were
observable fragmentation reactions, led Kalck to propose the working independently or if the complex was fragmenting to
bimetallic mechanism shown in Scheme 15. The mechanism generate active monometallic species. The hydroformylation
relies on several intramolecular hydride transfers, the first activity of a series of monometallic complexes (14) and spaced
which leads to formation of the Rhalkyl complex, the second bimetallic complexes (15) and (16) were studied. These were
CARBONYLATION PROCESSES BY HOMOGENEOUS CATALYSIS 15
R
R S
S Rh
Ph3P Rh PPh3
OC CO
+ H2
R
R S
Ph3P
S Rh
OC Rh PPh3
Aldehyde H H CO
+ Alkene
+ H2
R R
R S R S
Ph3P
PPh3 S PPh3
S OC Rh Rh
Ph3P Rh Rh CO
H H CO
OC H O
R
R
R
R S PPh3
Ph3P R S PPh3 Ph3P
S
S OC Rh Rh
OC Rh Rh CO + CO CO
O H
H
R
R
Scheme 15
+
R2 R3
P P R4
R1 Rh
(15)
CO O CO
Et2P C
Rh Rh PEt
C 2
P O
P
Aldehyde Ph Ph
+ H2
CO
R O
CO Et2P PEt2
Et2P H OC
Rh Rh PEt Rh Rh CO
C 2
P
O H P
P P H
Ph Ph
Ph Ph
+ Alkene
+ CO
Et2P PEt2
OC
Rh CO
Rh
P P H
R
Ph Ph
Scheme 16
Only the monometallic complexes, RCORh(CO)4, Rh4 (CO)12 , As a further development in the exploration of the role of
Rh6 (CO)16 , HMn(CO)5 and Mn2 (CO)10 , were observed during solvent in hydroformylation systems, the use of supercritical
the reaction. In addition, the kinetic data is consistent with carbon dioxide (scCO2 ), ionic liquids and fluorous systems
a unicyclic catalytic reaction mechanism (i.e. mononuclear has been reported. A review by Jessop, Ikariya, and Noyori
intermediates, equations 7 and 8). Product formation is presents information about the utility of scCO2 in a variety of
most probably due to interactions between a rhodium-acyl homogeneous reactions.59
intermediate, for example, RCORh(CO)4 , and a hydrido- Both modified and unmodified rhodium catalysts have
manganese species: shown good activity and selectivity for the hydroformylation
of 1-octene in scCO2 .60 With respect to the unmodified
HMn(CO)4 + RCORh(CO)3 RCHO + RhMn(CO)7 (7) catalyst, higher reaction rates can be achieved compared to
organic solvents or liquid CO2 under similar conditions. These
HMn(CO)5 + RCORh(CO)4 RCHO + RhMn(CO)8 (8)
modified systems exhibit higher regioselectivities compared
to conventional solvent systems.
The [RhMn] bimetallic system exhibits higher activity The hydroformylation of 1-hexene by supported ionic
for hydroformylation (500% higher) compared to the liquid catalysis (SILC) was recently reported by researchers
rhodium-only system. The presence of the manganese is at ExxonMobil.61 In this system, the active catalyst
responsible for a decrease in the induction period and prevents HRh(CO)(tppti)3 (tppti = tri(m-sulfonyl)triphenyl phosphine
deactivation via cluster formation. tris(1-butyl-3-methyl-imidazolium)) is contained within the
ionic liquid phase while excess tppti ligand is immobilized in
the support material. TOF values of 65 min1 were obtained
2.7 Novel Catalyst and Solvent Systems with silc while an unsupported biphasic ionic liquid medium
gave TOF values of 23 min1 .
New monodentate and bidentate phosphorus amidite (17a,
The utility of a biphasic fluorous system with
b) and phosphinite ligands (18a, b) have been synthesized
Rh(acac)(CO)2 /P(C6 H4 -4-OCH2 C7 F15 )3 as the catalyst pre-
and utilized as supporting ligands in the rhodium-catalyzed
cursor in the hydroformylation of 1-octene has been reported
hydroformylation of 1-octene in order to study electronic
by Bulto and coworkers.62 In this system, selectivities of
influences on the activity and selectivity of the reaction.58
99% and regioselectivities for the linear aldehyde up to
Monodentate ligands gave rise to systems with a moderate
linear/branched = 2.8 were achieved with TOF values of
selectivity for linear product while catalysts supported with
380 h1 . Although loss of rhodium was observed after the first
ligands with high -acidity resulted in an increase in reaction
run, the system could be recycled twice without diminishing
rate. Reactions supported by the bidentate amidite ligand gave
activity or selectivity.
both high activity and regioselectivity for linear aldehyde (l:b
100:1) and modest selectivity for isomerization (7%).
2.8 Silylformylation
OSiR3
higher yields (93 100%) of silylformylated products relative HSiR3/CO
to Rh4 (CO)12 . When HSi(OMe)3 was used as the silane, (9)
R [Ir], 50 bar R SiR3
only hydrosilylation was seen for the Rh4 (CO)12 , while 140 C
Co2 Rh2 (CO)12 gave some (20 40%) of the silylformylation
product. Only (Z)-1-silyl-2-formyl structures (19) were
found. In this case, alkene insertion into the IrH bond is likely
to occur first, producing a linear alkyl species. CO insertion
would produce an acyl species, which would then be followed
SiR3 by reductive elimination of the acylsilane product. Enolization,
followed by rapid reaction of HSiR3 with the OH group, traps
out the enol silyl ether. The H2 produced from this silylation
O H step is used to hydrogenate some of the starting alkene. Thus,
(19) the maximum yield will generally be only 66% of the enol silyl
ether product. The enol silyl ethers can be readily converted
into silyl ketones (equation 10).
As monometallic Rh complexes also catalyze this reaction
(although sometimes much more slowly) under conditions
where clusters are unlikely to form, it appears that only a OSiR3 acetone O
single-metal center is really required for this reaction. Ojimas aq. HCl (10)
CoRh(CO)7 catalyst has been studied in considerable detail R SiR3 25 C, 4 h
R SiR3
R
CO
OC CO
O SiR3 Rh
H OC SiR3
CO
+ Alkyne
+ CO
SiR3
OC H R
Rh OC CO
OC SiR3 Rh
CO OC SiR3
O R
+ HSiR3 + CO
CO
CO CO
OC CO OC CO
Rh Rh
OC SiR3 + CO OC SiR3
O R R
Scheme 18
CARBONYLATION PROCESSES BY HOMOGENEOUS CATALYSIS 19
OH HI
+ H2O
MeOH, H2O
OC CO
O Rh
I I
I + MeI
O
OC Me
OC OC CO
Rh Rh
I I I I
I I
+ CO
O
OC
Rh
I I
I
Scheme 19
Ph2P S CO O
Rh Rh
OC S PPh2 + LiI OMe + HI
MeI MeI
(21)
O O
Alternatively, LiI can react with methyl acetate to give MeI classes of compounds. These comprise iodide complexes of
and Li acetate. Carbonylation of MeI, again by [Rh(CO)2 I2 ] , transition and main group metals, such as zinc, cadmium,
produces acyl iodide, which can react with lithium acetate to mercury, indium, and gallium and transition metal carbonyl
produce acetic anhydride and LiI. The importance of LiI is complexes such as tungsten, rhenium, ruthenium, and osmium.
seen by the fact that at high lithium concentrations the rate A synergistic effect between the promoters and iodide salts
of the catalysis is first-order with respect to MeI and rhodium has also been observed at low water concentrations.
concentrations. This observation, once again, is consistent with Model studies76 in aprotic solvents have shown that
a rate-determining oxidative addition of MeI to the rhodium oxidative addition is 120 times faster with iridium complexes
catalyst. At low lithium concentrations the rate approaches than with the corresponding rhodium complexes while the
zero order in rhodium and methyl iodide, indicating that migratory insertion rate is higher for rhodium by a factor of
formation of methyl iodide from reaction of iodide and methyl 105 at 100 C than iridium. The migratory insertion step, which
acetate is now the rate-limiting step. Thus, the lithium iodide is rate-determining in the Cativa process, is enhanced by the
plays a very important role in the catalysis. Lithium is the most use of promoters, thus achieving a higher reaction rate. Batch
effective counter cation, with sodium being approximately 2.5 autoclave studies were carried out to explore the effect of
times slower. pCO, water, methyl iodide, and methyl acetate concentrations
The main difference between the Monsanto acetic acid on the reaction system. In addition, spectroscopic studies
process and Tennessee Eastman acetic anhydride process is have identified the key intermediate in the catalytic cycle
the presence of water in the acetic acid process, which produces as [Ir(CO)2 I3 Me] . The Sheffield University research group
HI and acetic acid. In both reactions, a small amount of H2 is headed by Maitlis and Haynes, in collaboration with BP
added to the CO stream to act as a reducing agent to keep the Chemicals, has published a comparison of both systems,
catalyst in the more active RhI oxidation state. An engineering where differences in the stability of this key intermediate,
problem with both processes is the highly corrosive nature of [M(CO)2 I3 Me] (M = Rh, Ir), are crucial to the reaction.79
the HI/iodide mixture, requiring the use of special chemically The increased stability of the iridium complex is related to
resistant alloys, pumps, and seals. the stronger metal carbon bond typically seen for iridium
compared to rhodium. Additional corroboration was obtained
from a static and dynamic density functional theory study
3.3 The BP Cativa Process of the migratory insertion step in methanol carbonylation,
[M(CO)2 I3 (CH3 )] to [M(CO)I3 (COCH3 )] (M = Rh, Ir),
For approximately 30 years, the most successful industrial
reported by Ziegler and coworkers.80
process for the carbonylation of methanol relied on an
In order to more fully understand the mechanism for
iodide-promoted rhodium catalyst. This technology, originally
the promotion of carbonylation in the Cativa process, a
developed by Monsanto and acquired by BP Chemicals in
recent comprehensive study utilizing spectroscopic methods
1986, is responsible for the majority of the acetic acid
and ab initio calculations was carried out to explore the
synthesized industrially. Since then, the most important
role of the promoters.81 The acceleration of the migratory
development in industrial carbonylation chemistry is the
insertion step is the result of iodide abstraction from the
Cativa process, announced by BP Chemicals in 1996.75
iridium center in fac,cis-[Ir(CO)2 I3 Me] by the promoters to
The Cativa process is based on a promoted iridium
yield the neutral species [Ir(CO)3 I2 Me] in the presence of
catalyst, and offers a considerable improvement over the
CO. It was determined that the migratory insertion of carbon
rhodium-based system as a result of increased catalyst
monoxide in [Ir(CO)3 I2 Me] is 700 times faster than for the
stability at lower water concentrations, decreased by-product
anionic species [Ir(CO)2 I3 Me] .
formation, higher rates of carbonylation, high selectivity
(>99% based upon methanol), and improved yields on carbon
monoxide.76 This is a more cost-effective process for methanol 3.4 Homologation of Carboxylic Acids
carbonylation owing to lower energy consumption and fewer
purification requirements. Implementation of this new process In 1981, Texaco announced the ruthenium/H2 /CO-
has now been achieved in four plants worldwide. catalyzed homologation of carboxylic acids. Homologation
Although the carbonylation of methanol using an iodide- refers to a chain-extension reaction that increases the carbon
promoted iridium complex was first reported by Monsanto number of the carboxylic acid (see Homologation Reactions).
researchers Roth and Paulik77 in 1968, and its mechanism The particular reaction that was initially studied was the
studied by Forster78 and others, it was the rhodium system conversion of acetic acid to propionic acid. The proposed
that was initially developed for commercialization. A more mechanism shown in Scheme 22 is based on a RuII /RuIV
complex mechanism for iridium, involving both anionic and cycle, similar to that suggested by Knifton and coworkers at
neutral intermediates was discovered, but it would take over Texaco.
twenty years to commercialize an iridium-based system The reaction conditions are somewhat more severe relative
for methanol carbonylation (Scheme 21). In the Cativa to the rhodium-catalyzed acetic acid process: >200 C
process, the iridium complex is promoted by two distinct and 100 250 bar 1:1 H2 /CO. The mechanism is not fully
22 CARBONYLATION PROCESSES BY HOMOGENEOUS CATALYSIS
H2 HI + CO HI H2
H2O + CO CO H2O + CO
HI HI
CO2 + 2HI [Ir(CO)3I] I [Ir(CO)2I2] CO2 + 2HI
CO
MeI
CO MeCOI
Neutral CO I Anionic
MeI
[Ir(CO)2I2Me]
[Ir(CO)2I2(COMe)] I
[Ir(CO)2I2Me]
[Ir(CO)3I2Me]
CO CO
Organic reactions
MeOH + HI MeI + H2O
Scheme 21
O
understood, because of the many-sided equilibria present and
O
the difficulty of mechanistic studies under the higher pressures
OH HI OH required. Labeling studies have confirmed that the carbonyl
group in the carboxylic acid product does indeed come from
+ H2O H2O
CO insertion into an alkyl species. Ruthenium is well-known
to heterolytically activate H2 (to give H on the metal and
O OC CO
free H+ ), and this cleavage may well be the route taken
Ru here. Protonation of the oxygen atom of the carbonyl group
O
I I I
I in conjunction with a hydride transfer to the -carbon would
I I lead one nicely to the proposed RuCH(OH)CH3 intermediate.
Repeating this same process would then give the RuCH2 CH3
O O alkyl species.
OC CO OC CO Interestingly, in spite of the fact that two equivalents of H2
Ru Ru
are formally required for a one-carbon atom homologation, the
I I I I
I I optimum yield of propionic acid occurs for a 1:1 H2 /CO ratio.
The additional hydrogen needed undoubtedly comes from a
+ H2
Ru-catalyzed Water Gas Reaction that converts some CO and
+ CO
H2 O into CO2 and H2 . CO2 is one of the side products observed
in this reaction. Additional homologation steps occur at higher
HO
temperatures and pressures. This homologation reaction also
OC CO OC CO appears to be quite general for higher-chain acids as the
Ru Ru
I I + H2 I I starting materials.
I I The potential industrial significance of this catalytic
reaction lies in the fact that acetic acid is readily synthesized
from Synthesis Gas (via methanol). The ability to homologate
Scheme 22
CARBONYLATION PROCESSES BY HOMOGENEOUS CATALYSIS 23
acetic acid to higher carbon chain acids means that industry 40 55 bar and 180 204 C using a NiBr2 /Cu halide catalyst
would not have to be dependent on petroleum feedstocks in THF solution. The details of the catalytic mechanism are
for longer chain carboxylic acid syntheses. The relatively not fully understood, but the core nickel-catalyzed cycle is
good hydrogenation ability of Ru, however, lowers the total shown in Scheme 23.
selectivity of the reaction by giving ethanol, ethane, and An interesting variant of the above reaction occurs when
propane as side products, along with ethyl acetate and allylic derivatives (halides, ethers, alcohols, etc.) are present
ethyl propionate ester products. Linear acids, however, are as well. 2,5-Dienoic acids are catalytically produced in high
the dominant products, with only traces of chain branching yields under ambient conditions.83,84
observed. HCo(CO)4 will also catalyze the hydrocarboxylation of
acetylene to produce acrylic acid, but under higher pressures
(100 200 bar, 100 C) an efficient second hydroxycarboxy-
3.5 The Hydrocarboxylation of Alkenes and Alkynes lation occurs to produce succinic acid in over 80% yield
(equation 14).
The reaction of an alkene (or alkyne), CO, and H2 O to
directly produce a carboxylic acid is called Reppe carbony-
lation chemistry or, more recently, hydrocarboxylation (see CO2H
Reppe Reaction). An excellent review of palladium-catalyzed HC CH + 2CO + 2H2O HO2C (14)
R OH HX
+ H2O
O OC CO
Ni
OC CO
R X + CO
CO
OC CO OC CO
R Ni Ni
X H X
O
+ CO + Alkene
OC CO OC CO
Ni Ni
R X H X
Scheme 24
Hydrocarboxylation reactions generally do not have reaction to yield either mainly branched or mainly lin-
very high regioselectivities when carried out with C4 ear product.
or higher alkenes, due to alkene isomerization side
reactions catalyzed by both acid and metal. Thus, COOH
many of the reactions done industrially involve sub- *
[Pd], H2C2O4
strates such as acetylene and ethylene where iso-
CO
merization side reactions will not present any prob-
(15)
lems. +
The regioselectivity of the palladium-catalyzed hydrocar- COOH
boxylation of styrene can be controlled by variation of the
phosphine ligand set.87 For monodentate phosphines, the
cone angle ( ) is an important consideration, whereas in
the case of chelating diphosphines the bite angle (n ) is
a controlling factor for the selectivity of the reaction. Pal- 3.6 Carboxylic Acids from Aldehydes:
ladium complexes comprising basic monophosphines such Amidocarbonylation
as PMe3 show no activity for the hydroxycarbonylation Oxidation of aldehyde products produced from hydro-
of styrene whereas 98% conversion and regioselectivities formylation is a major industrial route to carboxylic acids.
of up to 84% for the branched isomer can be achieved The Hoechst Celanese Corporation, for example, produces
with palladium complexes supported by PPh3 (equation 15). considerable quantities of linear C7 and C9 carboxylic acids
A preference for the formation of the linear isomer is from the Rh/PPh3 -catalyzed hydroformylation of 1-hexene
observed when diphosphines are employed in the reaction, and 1-octene.
although higher temperatures and pressures are required to Another route to carboxylic acids from aldehyde products
achieve similar activities to the corresponding monodentate (once again, generally produced via hydroformylation
systems (Table 7). Chelating diphosphines with bite angles catalysis) was discovered by Wakamatsu and coworkers. They
102 have exhibited the best activities for this reaction reported the carbonylation of aldehydes and primary organic
(95 99% conversion), while those with small bite angles amides to produce N -acylamino acids (equation 16).88 The
90 tend to give low conversions (5 28%). By modifying reaction is efficiently catalyzed by HCo(CO)4 at 100 C
the supporting ligand set and adjusting reaction conditions, and 140 bar of 3:2 H2 /CO (hydrogen is needed to help
it may be possible to influence the regioselectivity of the stabilize HCo(CO)4 ). Yields of over 90% of the appropriate
CARBONYLATION PROCESSES BY HOMOGENEOUS CATALYSIS 25
Table 7 Hydrocarboxylation of styrene with [PdCl2 (PhCN)2 ] carboxylic acids, esters, amides, and so on from organic
supported by monophosphines or diphosphinesa halides as shown in Scheme 26. The catalysis starts with a
Pd0 phosphine complex that dissociates a PPh3 to open up a
Branched:linear
Phosphine or n b ( ) % Conversion ratio coordination site in order to oxidatively add the organic halide.
Pd0 species are often electron-rich and reactive enough to
PPh3 145 96 84:16 undergo an oxidative addition to an aryl halide. Coordination
P(p-Tol)3 145 98 69:31
PPh2 (o-Tol) 161 76 100:0 of CO, followed by an alkyl migration, produces the acyl
dppe 78a 5 47:53 complex, which can react with a variety of reactants to produce
DPEphos 102a 99 14:86 the product of choice. Not shown in Scheme 26 is that the acyl
Xantphos 110a 99 19:81 complex will react with H2 to eliminate aldehyde products.
Carbonylation of aryl bromides with palladium catalysts
a
Reaction conditions: 4:1 monophosphine to Pd, 30 bar CO, 100 C;
10:1 diphosphine to Pd, 75 bar CO, 150 C. b Calculated bite angle. in aqueous solutions to produce carboxylic acids is a general
reaction. Typical reaction conditions are 100 130 C, 3 bar of
CO, 2 36-h reaction time using a PdCl2 (PPh3 )2 /PPh3 catalyst
N -acylamino acid can be obtained. This reaction has (0.1 1 mol%). A base, such as an amine, is needed in slightly
subsequently been referred to as amidocarbonylation and greater than stoichiometric quantities to trap out the HX acid
offers a viable alternative to the conventional Strecker reaction produced in the reaction. The presence of an acetamido group
(which uses HCN and NH3 ) for preparing -amino acids from ortho to the bromide significantly accelerates the reaction.
aldehydes.
Yields can be quite good, and there are usually no selectivity
problems with these types of oxidative addition reactions. One
O O O
H2O example reaction is shown in equation (17).
+
R NH2 H R R N R
O O
+ H2O + CO
(16)
NH NH
CO (17)
O COOH amine OH
MeO Br MeO
R N R
H O
There has been considerable interest from both academics Amides and esters are formed in good yields through
and industry in this reaction since 1980. There are a wide reaction of a primary or secondary amine or alcohol with
number of uses for the amido acid products: surface-active the Pdacyl complex. Amine reactions are, in general, more
agents and specialty surfactants (C10 C16 amido acids), rapid and give better yields of products compared to the
intermediates for aspartame sweeteners (phenylalanine), food alcohol analogs. Interestingly, -ketoamides can be formed
additives (monosodium glutamate), and chelating agents under the proper conditions (equation 18). The use of alkyl-
(iminoacetic acid and polyamido acids). Knifton (Texaco) or alkylarylphosphine ligands, higher CO pressures (10 bar),
has done extensive studies of this reaction,89 as have Ojima and lower temperatures (room temperature) favor the double
and coworkers.90 carbonylation. Long reaction times are often required, but high
The proposed mechanism is shown in Scheme 25.91 The yields can be obtained in many cases. The mechanistic details
coupling of this reaction with hydroformylation, for example, of this reaction are not fully understood, but it is probably not
allows the conversion of an alkene directly into an N - a double CO insertion. Rather, it is believed that reductive
acetyl product. Thus, the reaction of trifluoropropylene and elimination occurs from a double acyl species such as (22).
acetamide produces N -acetyltrifluoronorvaline in 80% yield
with 96% selectivity.
O O
ArX + 2CO + R2NH (18)
3.7 Carboxylic Acids from Organic Halides Ar NR2
O R
R N COOH
O O
H
+
R H R NH2
+ H2O
R CO
OC CO
Co O
O N
OC H
CO R N R
O R
+ H+
O
O R R
CO
OC CO N
Co N R
H OC CO
OC R Co
O H
OC
+ CO
CO CO
OC CO OC CO
Co Co
OC R OC N R
+ CO
O
R
HN
R O
O
Scheme 25
CO
Ph3P X
R Pd
PPh3
O
H2O RCOOH
O ROH RNH2 O O
R OH R O R
O O
R OR R NHR
+
Ph3P X
Pd
H PPh3
Scheme 26
The kinetic modeling study of 1-(4-isobutylphenyl)ethanol 4-iodotoluene (p-TolI) in the presence of carbon monoxide,
(IBPE) carbonylation using a homogeneous palladium triethylsilane, and the bimetallic [PdCo] system gave rise
complex has been reported by Chaudhari.94 The three key to p-TolCH2 OSiEt3 (76% yield, 85% conversion). Upon
steps (formation of the active substrate; formation of the addition of triethylamine, however, the product distribution
active catalyst; catalytic carbonylation of active substrate) changed to yield 1,2-di(p-tolyl)-1,2-bis(triethylsiloxy)ethane
were studied in detail. The average carbonylation rate as the major product (57% yield, 70% conversion), along
depends on several factors, so a dynamic analysis, where with p-TolCH2 OSiEt3 and p-tolualdehyde as minor products.
the concentrations of both the catalyst species and the Neither metal complex was an active catalyst on its own,
intermediates were varied, was carried out. therefore a synergistic effect is clearly at work here.
A two-phase system for the carbonylation of benzyl The corresponding PCy3 -supported palladium complex is
alcohol using a water-soluble palladium complex supported active in the hydroformylation of internal alkynes, although
by trisulfonated triphenylphosphine ligands (tppts = P(C6 H4 - higher activity can be achieved with the bimetallic system
m-SO3 Na)3 ) and a Brnsted acid cocatalyst has been reported [PdCl2 (PCy3 )2 -Co2 (CO)8 ]. The authors suggest a mechanism
by Sheldon and coworkers.95 The complex, [Pd(tppts)3 ] that involves two separate but linked catalytic cycles, each
is an effective carbonylation catalyst for benzyl alcohol based upon one of the two metals.
under mild conditions (100 C; tppts/Pd molar ratio: 12;
TsOH/substrate: 2). The only product obtained is phenylacetic
acid in 77% yield with 100% selectivity. This system has
also been applied to the carbonylation of IBPE to yield 4 KETONES
ibuprofen, which is currently prepared industrially using a
palladium/triphenylphosphine-supported catalyst in organic
4.1 Ketones from Alkenes and Alkynes
solvents. Although the selectivities are lower for the biphasic
system at this point, it is possible that further optimization of Ketones are sometimes seen as by-products in hydroformy-
the biphasic system will bring the selectivities up to current lation, particularly when the alkene concentration is very high
industrial levels in the future. and the H2 /CO pressure is low. This product is most favored
The catalytic silylative carbonylation of aryl iodides using for ethylene (producing diethyl ketone), but yields drop-off
a bimetallic catalyst system, [PdCl2 (PPh3 )2 -Co2 (CO)8 ], has quickly with higher-chain alkenes. It turns out that there are
been reported by Hidai and coworkers.96 The carbonylation of actually few good catalytic routes to acyclic ketones from
28 CARBONYLATION PROCESSES BY HOMOGENEOUS CATALYSIS
alkenes or alkynes. One of the best examples involves the high yields according to equation (22).101
reaction of butadiene with CO, an alkyl halide, and base,
which is catalyzed by [Co(CO)4 ] .97 The proposed mecha- R
nism is shown in Scheme 27. The reaction is highly regio- and R R R
stereospecific, with the acyl group always being added to the H2/CO (22)
least-substituted carbon of the least-substituted double bond. Co2(CO)8
O CO
OC CO
Co
R OC R
+ CO
+ RX
CO
CO
OC CO
Co OC CO
Co
R R
OC
O
O
CO
OC CO CO
Co
R
O
Scheme 27
CuCl2 need to be used to reoxidize the Pd0 back to PdII . The products. The 1,1-vinyl substrates require higher temperatures
carbonylation of halide-containing alcohols is a better reaction and pressures (70 C, 30 psi) for the cyclocarbonylation
as it takes place under mild conditions and often in good yields reaction.
(equation 25).
O
There has been more interest in the five-membered ring
systems which, as one might expect, generally give better Alkyne alcohols can be cyclocarbonylated to produce
yields. A general synthesis for aryl lactones with five- through lactones (equation 29). A PdCl2 /P(n-Bu)3 /SnCl2 catalyst
seven-membered rings is shown in equation (26). By using a system has been shown to be quite efficient for this reaction
primary or secondary amine, instead of an alcohol functional at 75 C and 8 bar CO pressure.105
group, the analogous lactams can be prepared. As with the
acyclic syntheses, the lactam preparations are somewhat more OH O
facile and give generally better yields. CO O
PdCl2(PBu3)2 (29)
O
O
X
CO, NR3
O (26)
Pd(PPh3)4 The proposed mechanism for this reaction is shown in
(CH2)xOH x Scheme 30. Coordination of the alcohol OH group to the
x = 1-3 PdII center causes deprotonation to produce the alkoxide-
coordinated species. CO insertion produces the alkoxyacyl
The cyclocarbonylation of vinylic halides (usually the species, which reacts with the alkyne group to produce the
bromide or iodide) is another route to lactones and lactams. cyclized vinyl Pd species, which is then protonated off the
1,2-Substituted vinyl compounds produce lactones where the Pd center.
double bond is incorporated into the ring (equation 27), while Pd will catalyze the ring expansion of azirines with
1,1-substituted vinyl substrates give an exo double bond CO to form bicyclic -lactams under mild conditions
(equation 28). The 1,2-substituted vinyl reactions can be run (equation 30). The Pd catalyst seems to always produce
under ambient conditions (24 72 h), producing high yields of the bicyclic complex shown in equation (30). Rh2 (CO)4 Cl2 ,
30 CARBONYLATION PROCESSES BY HOMOGENEOUS CATALYSIS
O O CO
[M] RH
M MCO
R H R MH R H
MCO
[M]
MCO O
Scheme 28
O O O
[PdCl2LL], CO
RX R C C Nu + R C Nu
NuH, Base
X
RX = C6H5X X
N X S X
L = phosphine
Scheme 29
however, will regioselectively ring-expand 2-arylaziridines to the basis of 1 H NMR experiments, the catalyst, BnCo(CO)4
the monocyclic four-membered lactam (equation 31). None (Bn = benzyl), is believed to dissociate the benzyl group to
of the isomeric lactam is produced in the rhodium-catalyzed generate a Co(CO)4 radical as the active catalyst.
reaction.106
R1 R1
R2
R1 N
N R2
CO R2 N [BnCo(CO)4] N
Pd(PPh3)4
(30) R2
R2 R1 N CO (200 psi)
(32)
O O O
R1 Ar Ar O
R1 R1 = H, Me; R2 = H, Me, Ph
R2 R2
Ar = Ph, m-F-Ph, p-tolyl, o-tolyl, thiophen-2-yl, furan-2-yl
N
CO (31)
RhCl2(CO)4 N N
R2
O R1 O R1 This area has been further advanced by Coates and
coworkers.108 The synthesis of succinic anhydrides by
-lactone carbonylation using a Lewis acidic cation in
Finally, ring-expanding carbonylation reactions using
conjunction with an anionic cobalt carbonyl complex has
cobalt have been reported by various groups. In the first
been reported (equation 33).
of these, the synthesis of 4,5-dihydro-1,3-oxazin-6-ones by a
ring-expanding carbonylation reaction of 2-aryl-2-oxazolines
with a cobalt catalyst has been reported by Xu and Jia.107 O O O O
This is the first example of the application of catalytic O [LnAl]+[Co(CO)4]
(33)
carbonylation to 2-oxazolines leading to the synthesis of an CO (200 psi)
important intermediate in peptide synthesis (equation 32). On R R R R
CARBONYLATION PROCESSES BY HOMOGENEOUS CATALYSIS 31
O
O OH
Pd
H+
H+
O OPd
O
Pd
+ CO
O Pd O Pd
Scheme 30
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32 CARBONYLATION PROCESSES BY HOMOGENEOUS CATALYSIS
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Cation-activated Enzymes the catalytic site. This type of modulation of protein function
by cations can therefore be considered to be the result of
allosteric (other site) interactions wherein binding to one
Jenny P. Glusker site affects the properties of a distant site in the enzyme
The Fox Chase Cancer Center, Philadelphia, PA, USA (possibly the active site). The cation, on binding, therefore
acts as an allosteric effector, and converts the enzyme from a
fairly inactive conformation to a conformation that manifests
appreciably increased catalytic activity.4
1 Introduction 1 Monovalent metal ions generally bind oxygen atoms that
2 Characteristics of Metal Ions Common in Cells 2 are found in the carboxylate groups of aspartate or glutamate,
3 Control of Cation Concentrations in Cells 3 the hydroxyl groups of threonine or serine, or the main-
4 Sodium- and Potassium-activated Enzymes 4 chain carbonyl groups of a protein. If the metal ions bind
5 Magnesium- and Calcium-activated Enzymes 7 directly to the substrate, they may serve to position it for
6 Summary 8 action. They can also act to stabilize some feature of the
7 Related Articles 8 protein structure.1 For example, many enzymes have open
8 References 8 and closed conformations, thereby controlling the access of
substrate to the active site. Activating cations may assist in
such control, perhaps modulating the conformational transition
between open and closed conformations.
Abbreviations
Identification of activating cations is often fraught with
PDB = Protein Data bank; PLP = pyridoxal 5 -phosphate; problems. It was pointed out by Markham that A difficulty in
E. coli = Escherichia coli. assessing the literature on monovalent cation activation of any
enzyme is that potentially interacting ions are commonly
present as counterions to the substrates and as buffer
components.6 This means that it is important to note if specific
precautions were taken to control the ionic environment of
the enzyme during study before concluding that the enzyme is
1 INTRODUCTION cation-activated in vivo. Recent X-ray crystallographic studies
of enzymes have provided much of the structural evidence
Cation-activated enzymes are those that require a cation we have for cation activation by monovalent cations. The
for maximal activity but for which that cation is generally location of the cation in the enzyme and its relationship to the
not a direct component of the enzyme reaction mechanism. active site are found by this method. Such monovalent cations
They were originally identified by Evans and Sorger in a are less likely than divalent ions to be directly involved in
study of activation of enzymes by monovalent metal cations.1 catalytic mechanisms and therefore their activating ability can
These activating cations convert the enzyme to a form with be identified more readily. There are, however, problems since
enhanced catalytic activity. When a cation is part of the enzyme ions such as Na+ are not appreciably better X-ray scatterers
mechanism, its requirement is essential and no reaction occurs than are water molecules (since the power of an atom to scatter
in its absence. On the other hand, if the enzyme is cation- X-rays depends on its atomic number, water 10, Na+ 10,
activated, the presence of the cation merely increases the NH4 + 11). For example, ammonium ions are commonly used
activity of the enzyme from a finite value, that is, the enzyme in crystallization of mother liquors. However, ammonium
generally works (but not as well) in the absence of the ions are difficult to identify except in very high-resolution
activating cation.2 A simple example, to be described here, is structures or those determined by neutron diffraction, where
provided by the activation of pyruvate kinase by potassium hydrogen atoms can be located, and therefore ammonium
ions that bind 6 8 A from the active site of the enzyme.3 ions differentiated from water molecules and sodium ions.
Reviews on aspects of the subject of cation-activated enzymes A method for identifying Na+ sites in proteins, involving
by Suelter,2 Woehl and Dunn,4 and Larsen and Reed5 are valence calculations based on interatomic distances, has been
highly recommended. proposed by Nayal and Di Cera.7
The cations involved in such activation are usually metal The activating cation presumably acts by helping the
ions or ammonium ions. Metal ions are generally utilized by protein to maintain a productive conformation, and examples
enzymes for a variety of reasons, of which the most important are provided by structural studies of enzymes that exhibit this
are to maintain the stereochemistry of the active sites of the property. Pauling suggested that complementarity between
enzymes, and to aid in electrophilic catalysis and electron- the structure of the enzyme active site and the transition state
transfer reactions. Metal ions that serve a cation-activating of the reaction is responsible for the lowering of activation
function in enzymes may be classified as cofactors because energies of enzyme-catalyzed reactions.8 Cation activation
they generally act by binding at sites distinctly separate from may aid this by ensuring that the active site has the correct
2 CATION-ACTIVATED ENZYMES
three-dimensional structure for as good complementarity as activating properties rarely, if at all, when K+ is exchanged
is possible, given the amino acid sequence of the enzyme. for Li+ .1
The activation may be accomplished by binding of the Biological effects are different for Na+ and K+ . The smaller
cation directly to the substrate, or binding at a distant ionic radius and therefore higher charge density on Na+
site. All gradations of these possibilities are encountered gives this ion a more favorable hydration free energy. The
in structural studies. Woehl and Dunn4 characterized two strength of the ligand field at the metal site and the ionic
types of mechanisms of cation activation of enzymes: those radius of the metal ion can provide part of the basis for
in which the cation plays a static structural role and, on selectivity in the metal ion binding to proteins. The four
binding, activates by stabilizing the conformation of the cations Na+ , K+ , Mg2+ , and Ca2+ are simple, each with a
enzyme that is catalytically active, and those in which the single oxidation state (+1 or +2). They lack easily excitable,
cation plays a dynamic role and, on binding, selectively unshared valence electrons. They bind ligands by electrostatic
acts to assist those enzyme conformational transitions that interactions rather than other types of binding and they are
can lead to complementarity between the active site and the classified as hard, because they are not readily polarized
transition state of the reaction to be catalyzed. Thus if a and are deformed only with difficulty (see Hard & Soft
cation binds selectively to the conformation of the enzyme Acids and Bases).10 They tend to bind to hard ligands,
that is complementary to the transition state structure for an notably those containing oxygen atoms. Ligands bind these
important step in the reaction being catalyzed, then activation cations less readily by way of nitrogen atoms and very rarely,
will occur. For example, Wells and Di Cera9 suggest that if at all, by way of soft sulfur atoms. Ammonium ions
when sodium binds to human -thrombin, an enzyme that it are the same size as Rb+ , similar to K+ . The monovalent
activates, there is a significant change in protein conformation. cations have weak positive charges and therefore would be
Woehl and Dunn4 remark that activation by such mechanisms expected to be more readily controlled. They are frequently
represents the fine-tuning of highly evolved catalysts. Because found near divalent cations, often with bridging ligands.
Na+ and K+ are ubiquitous in biological milieu, there is logic The positive charge of K+ in peroxidases may exert an
to the evolution of enzyme systems that take advantage of the electrostatic effect that can influence the redox properties of a
presence of these metal ions as activating cofactors. distant center.
Metal ions lose water from their hydration spheres
when they bind to complexing agents or to biological
macromolecules. The strength of binding of a monovalent
2 CHARACTERISTICS OF METAL IONS COMMON metal ion to a site on a protein molecule is determined by
IN CELLS the competition between water molecules and metal ions for
the site. Selectivity will occur as a result of ionic size and
Many cations are available for activation of enzymes. the strength and nature of the attractive forces in the protein
Among the most abundant in the body are the four cations site. For example, a large rigid cavity for binding would favor
Na+ , K+ , Mg2+ , and Ca2+ . They are found in living cells and a large cation, particularly if the directionalities of unpaired
extracellular fluids at millimolar concentrations. For Na+ and electrons in the cavity were appropriate for binding that metal
Ca2+ , the concentrations are intermediate between those in ion. Furthermore, shielding of the cavity from a solvent would
seawater and those in freshwater. Potassium ions are present in also be advantageous.
high concentrations in the cell (95% of the total potassium ions The four ions have different sizes, as shown in Table 1. Of
in the body are intracellular), and magnesium ions are found in these, magnesium is the smallest. In addition, the coordination
about the same concentration in both cells and the extracellular numbers of these cations, that is, the number of liganding
fluids around them. Cation-activated enzymes that are found atoms that can pack around the cation in the first coordination
within cells (where the K+ concentration is greater than sphere vary, ranging from six for magnesium to higher values
that of Na+ ) generally utilize K+ , while those outside the and near eight for potassium. Na+ and K+ , however, have
cell (where the Na+ concentration is greater than the K+ only a weak tendency to form complexes. On the other
concentration) utilize Na+ . For example, as will be described hand, Mg2+ and Ca2+ have moderate tendencies to complex
later, while most monovalent cation-activated enzymes prefer formation, particularly magnesium that has a high charge-to-
K+ to Na+ , the blood-clotting enzyme, thrombin, which is an radius value (the highest of any biologically important cation).
extracellular enzyme, prefers Na+ . Woehl and Dunn point out They are therefore utilized to an advantage in the action of
that the dissociation constants for Na+ and K+ binding are many enzymes.
well below the physiological concentration of these ions.4 This Proteins bind these four cations with strengths that depend
means that the binding sites for activating cations are saturated on the size of the cation and its charge. The higher the charge,
and their existence is a permanent feature of catalysis. In the better the cation binds; the binding of potassium and
general, it is found that activating properties are maintained sodium ions is poorer than that of magnesium and calcium
if K+ is replaced by NH4 + and Rb+ . The replacement is ions. The size is also important and a protein often provides
poor for an exchange with Na+ and succeeds in maintaining a pocket of the correct size so that it can distinguish between
CATION-ACTIVATED ENZYMES 3
The control of K+ is illustrated by the 3.2 A crystal structure Na+ concentration is not high enough to saturate the site. A
of a potassium channel.18 This allows potassium ions but decrease in Na+ reduces fibrinogen cleavage and therefore
not sodium ions to diffuse through a lipid bilayer that they slows the clotting time.
would not normally permeate. An X-ray diffraction analysis Thrombin binds sodium better than potassium. The cation
has shown that the channel resembles an inverted tepee is bound by backbone carbonyl groups of Arg221a and Lys224
or cone with the wide part opening to the outside of the and by four buried water molecules.21,22 One water molecule
cell membrane. This wide part is, however, almost filled by connects the sodium ion to OD2 of Asp819; this accounts
membrane-spanning -helices that provide dipoles that aid for the primary specificity of the enzyme. When sodium is
K+ movement through the channel and a selectivity filter released, Asp819 reorients and this perturbation extends to the
that provides a narrow opening with a diameter adjusted to catalytic site.
favor K+ and repel Na+ . As K+ enters, it is dehydrated and It is not necessarily the strength of monovalent cation
coordinates to main-chain carbonyl groups. The pore is long binding that determines the activating ability. This was
enough to accommodate two K+ that repel each other so that demonstrated by Di Cera and coworkers.23 They were able
the inner one progresses into a wider aqueous chamber and on to convert thrombin from a sodium-specific enzyme to a
to the interior of the cell. potassium-specific enzyme. This was done by site-directed
mutagenesis by redesigning a loop in the backbone that defines
the geometry near the cation-binding site and controls access
to it. They found, however, that, while the mutant enzyme
4 SODIUM- AND POTASSIUM-ACTIVATED bound K+ better than Na+ , it was still preferentially activated
ENZYMES by K+ rather than Na+ .
The crystal structures of several sodium- and potassium- 4.2 2,2-Dialkylglycine Decarboxylase
activated enzymes have now been determined and the position
of the monovalent cation established. Structural data are This enzyme catalyzes a decarboxylation and transamina-
listed in the Protein Data Bank (PDB).19 They provide a tion converting 2,2-dialkylglycine with pyruvate into a ketone,
clue (but not an absolute proof ) to their location within the L-alanine, and carbon dioxide. It is activated by K+ and inhib-
enzyme on activation. Further biochemical studies may be ited by Na+ and Li+ . The enzyme has a structure made up
necessary to verify this finding. Some examples of these of a dimer of dimers. The catalytic site is near the interface
structures are presented here. The first example (thrombin) between monomers of the dimeric unit and involves residues
is a sodium-activated enzyme, but the others are potassium- from both subunits.2426 There are two monovalent cation
activated enzymes. sites per monomer, one structural and the other regulatory.
The regulatory K+ causes changes in the active site, especially
near Ser80 and Tyr301. Crystal structures have been reported,
4.1 Thrombin one with K+ and Na+ , another with two Na+ in the metal
ion sites and the results were compared. Hohenester showed
Thrombin, the final enzyme in the coagulation cascade, is that Li+ behaves like Na+ , while Rb+ behaves like K+ . When
a serine protease that causes blood clotting. It cleaves and potassium is replaced by sodium, the link to Ser80 is lost
converts fibrinogen to an insoluble fibrin clot so that wound and its hydroxyl group is replaced by water. This change is
repair can commence. It can also behave as an anticoagulant caused by the ion size and coordination number. It results in
when protein C is brought into the picture. The enzyme a large change in conformation and a change at the catalytic
cleaves at specific arginine residues aided in its selectivity by site. Na+ or Li+ binding at the regulatory site is strongly
nearby sites on the enzyme. Human -thrombin is a sodium- inhibitory because of insertion of extra water molecules as
activated enzyme, in that its activity is greatly increased in metal ion ligands.
the presence of Na+ . Wells and Di Cera9 point out that the
blood stream concentrations are higher for Na+ than K+ and
that thrombin has adjusted to this environment. The binding 4.3 Pyruvate Kinase
of monovalent cations has been shown spectroscopically to
facilitate a change in the conformation of the enzyme. Na+ Pyruvate kinase catalyzes the conversion of phospho-
switches the enzyme between two conformational states, one enolpyruvate and ADP to pyruvate and ATP. A proton is
of which activates fibrinogen and the other cleaves protein C. taken up in the reaction. The enzyme binds one K+ and two
This function is referred to as an allosteric switch because Mg2+ ions. The 2.9 A crystal structure shows that the K+
the Na+ converts the thrombin from a slow (Na+ -free) interacts directly with the migrating phosphoryl group and
form that cleaves protein C to a fast (Na+ -bound) form indirectly with residues in the active site.27,28 Activity with
that enhances substrate binding and fibrinogen cleavage.20 Na+ is about 9% that of K+ . Figure 1 shows the geometry of
Both forms are normally found in the blood because the the active site. Oxalyl phosphate is a substrate for pyruvate
CATION-ACTIVATED ENZYMES 5
kinase and the ATP-oxalate complex (shown in the figure) is 4.4 Diol Dehydrase
the product of the reaction. Each oxygen atom of the -ATP
interacts with a metal ion, and it is possible that this prepares Diol dehydrase is a bacterial enzyme that catalyzes the
dehydration of 1,2-diols to aldehydes. The structure at 2.1 A
the phosphorus for nucleophilic attack. One oxygen atom of
showed that the enzyme binds K+ .30,31 The K+ has seven
the oxalate is 3 A from the -phosphorus of ATP, and is
ligands: the two hydroxyl groups of the substrate, propane-1,2-
in position for an in-line transfer of the phosphoryl group
diol, and five oxygen atoms of active-site residues. It is thought
from ATP to oxalate. This alignment is aided by the metal
that the K+ positions the substrate within the active-site cavity
ion binding. and also provides space between radical intermediates and
Many pyruvate kinases show the active-site geometry amino acid residues in the active site, thereby protecting the
illustrated in Figure 1, but others, such as those from enzyme from radical attack. The K+ may also participate in
Escherichia coli and Corynebacterium glutamicum do not the migration of the hydroxyl group on C2 to C1 of the radical
require monovalent cations for activation. In these, Glu117 form of 1,2-propanediol. The structure of glycerol dehydrase
in the K+ binding site is replaced by lysine. This lysine has approximately the same features.32
behaves as an internal monovalent cation, that is, a tethered
ammonium ion, for which the single positive charge takes
4.5 Inosine Monophosphate Dehydrogenase
the place of K+ .29 Significantly, this experiment provides
confirmation of the activation site of K+ . In inosine monophosphate dehydrogenase, the monovalent
metal ion accelerates the hydride transfer step of the reaction
with apparently few other effects on the enzyme structure.
Probably the monovalent cation is involved in helping position
the nicotinamide cofactor. The active site and location of the
potassium ion are shown in Figure 2.33 Mycophenolic acid
in this diagram is an inhibitor that is thought to lock inosine
monophosphate into the active site, as shown. Note the large
distance between the inhibitor (in the active site) and the K+ .
4.6 Tryptophanase
ATP
This enzyme cleaves L-tryptophan to give indole, pyruvate,
P and ammonia by -elimination and deamination. It is activated
by various monovalent cations, especially ammonium
ions (NH4 + > K+ > Cs+ > Na+ > Li+ ).4 The enzyme is a
Mg2 tetramer. Its catalytic sites, as well as the K+ -binding sites, lie
P
P Water
Cys331
s Gly501
K
Gly502
Gly326
K Glu500
Figure 1 The active site of pyruvate kinase, drawn from PDB file
1A49, showing bound Mg2+ , K+ , ATP, and oxalate.28 The bonds of
the oxalate and the -phosphate of ATP are black. Mg1 is coordinated
by two oxygen atoms of oxalate, one of the -phosphate of ATP, Oxidized IMP
oxygen atoms of Glu271 and Asp295, and one water molecule.
Mg2 is coordinated by three oxygen atoms of ATP and three water
molecules. K is coordinated to the carbonyl group of Thr113, Ser76,
Asp112, Asn74, the -phosphate of ATP (as shown), and a water Figure 2 The active site of inosine monophosphate dehydrogenase,
molecule. Note that the K+ interacts with a substrate. In this and drawn from PDB file 1JR1.33 This shows the inhibitor mycophenolic
Figure 2, drawn with the program ICRVIEW,54 atoms of O are acid at the active site, stacking against PLP. The K+ site is distant
stippled, of N are filled, and of C are open from the active site
6 CATION-ACTIVATED ENZYMES
Tyr301 Tyr72
Lys266
HO OH
H2O
+
N
PLP O
O H2
P
O O N Gln99
O
O
NH +
H3 N
Lys265
O O
H2O
O O O Gly53
Asp223 Glu70 +
K
O
O
H2O H2O
Asn271
Figure 3 Diagram of the active site of tryptophanase34 showing the large distance between the K+ and the active site. The distance between
K+ and N1 of PLP is 15.5 A
at the interface of two subunits.34,35 The crystal structure at cation for activity. K+ does not play a direct role in binding the
2.1 A resolution shows that the K+ site is about 6 A from the substrate or cofactor but changes some side-chain orientations.
active site and 18 A from the nearest pyridoxal 5 -phosphate The -subunit cleaves 3-indole-D-glycerol 3 -phosphate to -
(PLP, vitamin B6 ) ring.34 The K+ is bound to the enzyme glycerolphosphate and indole. The -subunit replaces the
by backbone carbonyl oxygen atoms of Gly53, Glu70, and -hydroxyl of L-serine by indole to form L-tryptophan. In
Asn71, a side-chain carboxylate group from the same Glu70 the reaction, the -subunit catalyzes the conversion of 1-
and three water molecules; Glu70 is in a different subunit from (indol-3-yl)glycerol 3-phosphate to indole and glyceraldehyde
the other protein ligands. This is diagrammed in Figure 3. In 3-phosphate. The indole then migrates to the -subunit where,
this way, both the K+ and the PLP contribute to the stability with serine in the presence of pyridoxal 5 -phosphate, it is
of the catalytic dimer. It appears that K+ binding stabilizes converted to tryptophan. The crystal structure of tryptophan
the ground state of the quinonoidal form of the PLP-enzyme synthase at 2.8 A resolution showed that the active sites of
complex and lowers the activation energy for a subsequent the - and -subunits are about 25 A apart.37,38 The two sites
-proton abstracting step, that is, the conversion of an external are connected by a largely hydrophobic intramolecular tunnel
aldimine Schiff base to the quinonoid form. By contrast, Na+ with dimensions sufficiently large to accommodate up to four
does not behave in this way, which may explain why it is molecules of indole. It was found from further studies that
less efficient at activating. This is in line with spectroscopic the tunnel could be blocked by the side chain of Phe280. It
evidence. A bound coenzyme gives a spectrum with peaks appears that various monovalent cations cause movements of
at 337 and 420 nm. In the presence of K+ , this spectrum Phe280 out of the tunnel, implying that Phe280 can act as a
changes with pH, but not in the presence of Na+ .35 Tyrosine gate to control passage through the tunnel.
phenol-lyase cleaves L-tyrosine to give phenol, pyruvate, and
an ammonium ion. This enzyme is like tryptophanase.36 The
4.8 Other Potassium-activated Enzymes
metal ions add to subunit interactions and in the absence of
metal the enzyme dissociates to monomers. Many crystal structures of other potassium-activated
enzymes have been reported. They generally require a
4.7 Tryptophan Synthase divalent cation and are activated by a monovalent cation
that also binds. Such enzymes include amylase,39 which has
Tryptophan synthase catalyzes the last two reactions in the a unique CaNaCa trinuclear center, S-adenosylmethionine
biosynthesis of L-tryptophan. This enzyme needs a monovalent synthetase,40 E. coli methionine aminopeptidase41 in which
CATION-ACTIVATED ENZYMES 7
the K+ is 13 A from a dinuclear metal center and rhodanese,42 charges would tend to repel the electron pairs of the
Class II fructose 1,6-bisphosphate aldolase,43,44 ascorbate attacking nucleophile, especially those with anionic character.
peroxidase that contains a K+ cation that has a profound DNA polymerase requires magnesium to provide the proper
influence on the redox properties of the heme group,45 and conformation of the arriving nucleotide triphosphate for
cytochrome P450cam that binds camphor more readily when incorporation into nascent DNA in a 5 to 3 direction.
K+ is present, possibly due to stabilization of the environment When magnesium is replaced by manganese, there is an
of Tyr96.46 In carbamoyl phosphate synthetase, which also increase in the speed of replication and a decrease in
requires K+ , Glu214 bridges the K+ and ADP forming a the precision of the operation. Thus, nature has opted
K loop that allows communication from K+ to the active for magnesium throughout nucleic acid enzymology to
site via the carboxylate of this glutamic acid.47 In the heat- maximize fidelity at the expense of speed in transmitting
shock protein Hsc70, two potassium ions are bound in the the genetic code.
nucleotide-binding site.48 The function of magnesium in enzyme activity may
either be to form a complex with the substrate, as in the
magnesium-ATP complex formed in creatine kinase and
phosphofructokinase, or to bind to the enzyme and either
5 MAGNESIUM- AND CALCIUM-ACTIVATED produce an allosteric activation or play a direct role in
ENZYMES catalysis. If an enzyme is known to utilize a nucleotide as
one of its substrates, it can be assumed that magnesium is also
Activation by divalent cations is more difficult to assess required for catalysis. The magnesium ion possibly acts as an
because divalent cations are often integral parts of the electrostatic shield. The enzyme pyruvate kinase, described
enzyme mechanism. Some of the guidelines for determining earlier, and shown in Figure 1, requires both magnesium and
whether a cation activates enzymes were given above. About potassium ions for maximal activity.
60 65% of total body magnesium is in bone and 27% in
muscle. The remaining is in living cells and extracellular
fluids. The insolubility of calcium phosphate has meant that
5.2 Alkaline Phosphatase
calcium is unsuitable as an intracellular cation. This leaves
magnesium as the major intracellular ion for the complexation
of phosphate. Magnesium ions are used as cofactors in One example of a magnesium-activated enzyme is E. coli
phosphate transfer, to carry out the transfer of substituted alkaline phosphatase. This is a zinc-binding enzyme with a
phosphoric acids. Examples are provided by kinases (that high pH optimum (hence the name) that catalyzes phosphoryl
transfer phosphoryl groups between ATP and a metabolite), transfer to various alcohols. When a phosphomonoester binds
synthetases, and phosphatases. They also catalyze the transfer to the active site, a serine hydroxyl group (Ser102) is
of acyl groups, hydration-dehydration or tautomeric reactions, phosphorylated and the product alcohol leaves. The enzyme
carbonyl addition reactions, and dehydrogenases. Magnesium binds one magnesium and two zinc ions per active site.50
with its double positive charge neutralizes anionic centers A crystal structure shows the phosphate group bound by
in proteins, particularly phosphate and carboxylate groups. arginine and the two zinc ions. The magnesium ion is bound
Magnesium ions are smaller than calcium ions and bind to Asp51, Glu322, Thr155, and three water molecules. Both
with a coordination number that is generally six, while the zinc ions bind to the phosphate group and one (Zn2) also
coordination number of calcium is seven or eight. Thus, binds to Asp51. Lys328 is constrained by Asp153, which
Mg2+ can fit in Ca2+ holes, but the opposite is not true. binds to a magnesium-bound water molecule. The importance
Often calcium binds both oxygen atoms of a carboxylate of Asp153 is evident. Replacement of this aspartate by
group (bidentate binding), but when magnesium takes its histidine (Asp153His) is found to give an enzyme that binds
place only one of the oxygen atoms is bound to the three zinc ions, no magnesium.51 This third site (Zn3) is
metal ion. tetrahedral rather than octahedral as found when magnesium
is present. The result is that Zn3 is bound by Asp51, Glu322,
Thr155, and His153 but the link of Asp51 to Zn2 is lost,
5.1 Magnesium
as is the constraint of Lys328 by Asp153. Therefore Lys328
The features of magnesium ions that are of particular binds to the phosphate, and the hydroxyl group of Ser102
significance are their strong affinity for water and their rigid interacts with Zn2. This means that the all-important Ser102
octahedral coordination sphere which suggest they may be has decreased activity as a nucleophile as a result of the
used to deliberately prevent motion in certain regions of mutation, and the resulting enzyme (Asp153His) is inactive.
the enzyme system and also to orient functional groups However, when excess magnesium is added it regains activity.
as needed for catalysis.49 Magnesium shields the negative In this example, the activating power of magnesium is
charges of the phosphate groups because otherwise these evident.
8 CATION-ACTIVATED ENZYMES
5.3 Klenow Fragment of DNA Polymerase essential component of the reaction is not clear, especially
when the activating cation is divalent. Further structural and
In the Klenow fragment of DNA polymerase I (the 3 ,5 - biochemical studies will clarify this subject.
exonuclease), two metal ions are used.52 One stabilizes the
transient pentacovalent species and the leaving of a 3 oxyanion
(Mg2+ ), and the other facilitates the formation of an attacking
water molecule or hydroxyl group (Zn2+ ).
7 RELATED ARTICLES
5.4 Calcium (See Calcium-binding Proteins)
Ninety-nine percent of the calcium and 85% of the Biomineralization; Calcium-binding Proteins; Metal Ion
phosphorus in the body are found in bones, mostly a poorly Toxicity; Metal-mediated Protein Modification; Metalloreg-
crystalline hydroxyapatite Ca10 (PO4 )6 (OH)2 . In addition, ulation; Nucleic Acid Metal Ion Interactions; Nutritional
calcium is involved in blood coagulation and is an intermediary
Aspects of Metals & Trace Elements.
factor between impulses and muscle contraction. Calcium has
an activating effect on enzymes such as phosphorylase kinase
and pyruvate dehydrogenase (lipoamide)-phosphatase.
In small organic structures, the coordination number of
calcium varies from 6 to 10. The geometry of this coordination
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276, 603. from the National Institutes of Health and by an appropriation
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Chalcogenides: Solid-state to give rise to strong sp3 hybridization and more rigid angular
requirements.
Chemistry As we move down group 16, the elements acquire an
increasing tendency to catenate, that is, to form homoatomic
bonds creating chains. This results not only in rings or
Mercouri G. Kanatzidis chains in the several elemental forms known, but also in the
Michigan State University, East Lansing, MI, USA polychalcogenide Qn 2 (Q = S, Se, Te; n = 2 7) ions that
can exist in solution or in the solid-state.79 The fascination
Based in part on the article Chalcogenides: Solid State Chemistry by of chemists with the chalcogen group has many reasons, not
Patricia M. Keane which appeared in the Encyclopedia of Inorganic the least of which is the ability to form intriguing polyanions
Chemistry, First Edition.
and polycations.
Sulfur and selenium have several allotropic forms with
the rings of S8 and Se8 being the most known. Tellurium
1 Introduction 1
is polymeric with no known allotropes. The discovery of
2 Binary Compounds 1
3 Ternary Compounds 5
the cyclo-octatellurium ring (Te8 ) in Cs3 Te22 ,10 represented
4 Quaternary Compounds 25
a landmark in chalcogen chemistry as it completed the
5 Concluding Remarks 35 chalcogen series S8 , Se8 , and Te8 . Indeed, Te8 has the expected
6 References 35 puckered ring structure. Although not a true allotrope, since
it coexists with other components in Cs3 Te22 , Te8 has been a
missing species and had caused chemists to wonder about its
stability.
Chalcogenides of the transition and main group metals
can exhibit useful physical and chemical properties that
are intellectually stimulating, scientifically interesting, and
1 INTRODUCTION often useful for applications in a variety of technological
fields. Some examples include optical information storage
The class of chalcogenide compounds is large and its devices,11 thermoelectric devices,1214 radiation detectors,15
members contain combinations of various elements with the nonlinear optics,16 thin film electronics,17 solar energy
chalcogens, that is, sulfur, selenium, and tellurium. Oxygen conversion devices,18 catalysis,19 spintronics,20 and even
is not included because it has a distinct and vast chemistry superconductivity.21 Binary and ternary chalcogenides have
of its own and it must be dealt with separately. Solid-state been more extensively investigated than quaternary chalco-
chalcogenides generally refer to those compounds whose genides however the latter also exhibit interesting properties.
structure involves extended frameworks and it is to be Not surprisingly, therefore, during the last decade the chem-
distinguished from another class of chalcogenide compounds istry of quaternary chalcogenides has witnessed the largest
that involves discrete molecular species. This section aims growth.22 Indeed, we have seen an impressive expansion in
to introduce the reader to solid-state chalcogenides with solid-state chalcogenide chemistry with emphasis in mate-
particular emphasis given to the developments of the last rials with new compositions and structure types. In this
decade. It is not meant to be an exhaustive review article but regard, the emergence of novel synthetic methodologies
such as flux and solventothermal techniques has played a
an entry point to this area of inorganic chemistry. Therefore
major role. Unfortunately, the physical properties of many of
many interesting results will be left out. Several important
these new chalcogenide materials have not yet been investi-
review articles have appeared on the subject which, when
gated.
taken collectively, capture most of the research activity of the
In this article, we will present selected developments in
last decade.16
chalcogenide solid-state chemistry of the past decade. We will
There exist large structural and chemical differences
begin from the simple binary systems and evolve towards
between the class of oxides that is huge and the smaller class of
more complex systems.
chalcogenides. Why are oxides different from chalcogenides?
Part of the answer lies in the ability of the oxide ion (O2 )
to adopt almost any MOM angle from very small (e.g. 80
deg) to 180 deg. In contrast, the chalcogenide ions (Q2 )
do not, and prefer a much smaller range of MQM angles. 2 BINARY COMPOUNDS
This can be explained by the more extensive hybridization
of s-p orbitals in S, Se, and Te relative to those of oxygen. The binary group of compounds can be divided into three
In oxygen, s-p mixing does not occur readily because of the major subgroups (a) alkali and alkaline earth metal chalco- and
large energy gap between the two orbital levels. In the heavier polychalcogenides, (b) valence-precise metal chalcogenides,
congeners, the s-p levels come increasingly closer in energy and (c) metal-rich chalcogenides.
2 CHALCOGENIDES: SOLID-STATE CHEMISTRY
Te(3)
Te(3)
Te(4)
Te(3)
Te(3)
b
a
(a) (b)
Looking down the b-axis (Figure 5), one can see the layers of
Se stitched together by eight-coordinate Eu atoms. Looking
down the c-axis in Figure 5, one can see rows of diselenide
dumbbells. These rows are packed together in a staggered
fashion and run parallel to the c-axis, separated by rows of
Eu atoms. Each Eu atom is bonded to eight Se atoms in a
square antiprismatic coordination. The diselenide dumbbell
sits inside of a rectangular, parallelepiped pocket, shown in
Figure 5. The structure of EuSe2 is closely related to that of
the ternary KCeSe4 , which is also tetragonal.29 We can view
the latter compound as deriving from EuSe2 by substituting
two Eu2+ ions with a K+ and Ce3+ ion respectively. EuSe2
is a semiconductor, with a well-defined energy gap, Eg , of
1.43 eV. It also behaves as a bulk antiferromagnet with a
metamagnetic transition below 8 K.
x
z y
(a) (b)
Figure 4 The structure of the high-pressure form of B2 S3 . (a) A polyhedral representation of the three-dimensional framework (b) an excised
fragment from the structure showing the adamantane-type superclusters
4 CHALCOGENIDES: SOLID-STATE CHEMISTRY
y x
z x
z
(a) (b)
Figure 5 The structure of EuSe2 viewed down (a) the c- and (b) the b-axis direction. Black atoms are Eu
physical aspects. The fertile nature of this area is illustrated markedly from those of the known binary sulfides. (Nb, Ta)7 S2
by the discovery of several interesting binary compounds forms a structure of its own type comprising distorted M13
within the past decade. The factors controlling the structural icosahedra. The structure of (Nb, Ta)7 S2 is composed of six
anisotropy of a new class of tetragonal layered compounds crystallographic inequivalent atoms: Ta(1), M(1) M(4) with
that includes Ta2 Se, Ta2x Nbx S, Hf3 Te2 , and the ternary M representing Nb or Ta, and S(1). Ta(1), M(2) and M(4) lie
ZrZTe (Z = Si, Ge, Sn) have been discussed.35 Examples in mirror planes at y = 1/4 and 3/4. The other atoms occupy
of reduced binary chalcogenides of the earlier transition general sites. Figure 7 shows a projection of the structure
metals include M8 Te3 (M = Sc, Y),36 Sc9 Te2 ,37 Ti8 Q3 onto the bc plane. Nbx Ta7x S2 forms a unique pentagonal
(Q = S, Se),38 Lu8 Te,39 Lu7 Te,39 Ti11 Se4 ,40 Zr3 Te, Zr5 Te6 ,41 antiprismatic columnar structure which as opposed to
ZrTe,42 Hf2 Te,34 Hf3 Te2 ,43 Nb21 S8 ,44 Ta2 Se,45 Ta97 Te60 ,46 the related structures of the Ta-rich sulfides contains one
Ta181 Te112 ,47 and Ti9 Se2 .48 Of these, the phases Ti9 Se2 , additional metal site at which Nb accumulates. This facilitates
Ti11 Se4 , Hf3 Te2 , Ta2 Se, and the tantalum tellurides account an energetically favorable partial segregation of Nb outside
for new, previously unknown structure types. The more metal- the metallic columnar core.
rich chalcogenides generally contain more condensed metal The chemistry and metal metal bonding is further enriched
substructures, often in the form of corrugated sheets composed and enlarged by the addition of late transition metals that
of condensed octahedra that are separated by chalcogen atoms. stabilize new metal frameworks (see below).
Hf3 Te2 and Ta2 Se represent layered materials with bcc-like
metal stacks coated on both sides with chalcogen atoms. Lu8 Te
and Lu7 Te represent an extreme example of a metal-rich phase
which can be regarded as novel substitutional derivatives of 3 TERNARY COMPOUNDS
lutetium metal. Another very metal-rich phase is Sc9 Te2 which
shows a two-dimensional distortion wave. The ternary group of compounds can be divided into three
Differences in the cohesive energy between Nb and Ta major subgroups (a) alkali and alkaline earth metal chalco- and
give rise to the formation of a bundle of (Nb, Ta)-rich polychalcogenides, (b) valence-precise metal chalcogenides,
sulfides without counterparts in the corresponding binary and (c) metal-rich chalcogenides.
MS systems. The phase richest in metal of this class has
been identified as Nbx Ta7x S2 .49 (Nb, Ta)7 S2 is an excellent
example of a mixed niobium tantalum-rich sulfide without 3.1 Compounds with Alkali and Alkaline Earth Metals
counterpart in the adjoining binary systems. Its structure differs
This subclass has seen rapid growth during the past decade.
Compounds in this category can be conveniently viewed as
pseudo-binary networks of metal chalcogenide anions which
M3 M3 M3 M3 are charge-balanced with electropositive alkali or alkaline
M1 M1 S1 S1 M1 M1 earth cations. The interactions between the electropositive
cations and the [Mx Qy ]n macro-anions are generally regarded
M2 Ta1 M2 M4 M4 M2 Ta1 M2
to be electrostatic in nature. These compounds are normally
M1 M1 S1 M1 M1 prepared by direct combination reactions of simpler reagents,
S1
via the solventothermal method or by the polychalcogenide
M3 M3 M3 M3 M3 M3
flux technique. The rationale behind the solventothermal
S1 S1 M1 M1 S1 S1 method or alkali polychalcogenide flux technique has been
explained in detail earlier.4,5,50,51 Intercalation and ion-
M4 M4 M2 Ta1 M2 M4 M4 exchange chemistry as well as electrochemistry are also useful
in preparing compounds at low temperatures that may not be
S1 S1 M1 M1 S1 S1
accessible at higher temperatures.
M3 M3 M3 M3 Topotactic ion-exchange reactions can be used to prepare
M3 M3
M1 M1 S1 S1 M1 M1 metastable materials. The use of alkali halides to form other
alkali metal ternary chalcogenides has been used widely.
M2 Ta1 M2 M4 M4 M2 Ta1 M2 The formation of other alkali topotactic derivatives from
KBi3 S5 52,53 is an example of such chemistry (equation 1).
M1 M1 S1 S1 M1 M1 b
M3 M3 M3 M3 KBi3 S5 + xs-AI ABi3 S5 + KI (1)
c A = alkali metal
Figure 7 The structure of Nb2.73 Ta4.23 S2 projected down the a-axis. The KBi3 S5 possesses an open framework composed of
(Reprinted from Ref. 49. 2002, with permission from Elsevier) edge-sharing BiS6 octahedra to form large parallel tunnels
6 CHALCOGENIDES: SOLID-STATE CHEMISTRY
Figure 9 Comparison of the structure of ZrSe3 and two intercalated versions Rb0.86 Zr2 Se6 and Cs0.80 Zr2 Se6
CHALCOGENIDES: SOLID-STATE CHEMISTRY 7
z x
Ag
z
Ba
y x
K2 Cu5 Te5 ,60 K4 Cu8 Te11 ,61 A3 Cu8 Te10 ,62 A2 BaCu8 Te10 (A =
Rb, Cs) whose characteristic structural feature is the
pentagonal dodecahedral [Cu8 Te12 ] cluster.62 A3 Cu8 Te10 and
A2 BaCu8 Te10 are isostructural and contain the same layered
Cu/Te framework built from fused [Cu8 Te12 ] pentagonal
dodecahedral cage-clusters (Figure 13). The quaternary phase
derives from the ternary one by a substitution of a single A+
ion for a Ba2+ ion. The structure is layered and consists of
condensed pentagonal dodecahedral clusters sharing TeTe
edges. Each Cu8 (Te2 )6 dodecahedral cluster endohedrally
encapsulates an alkali or Ba2+ ion. The Cu8 (Te2 )6 cluster
is also the building block of K4 Cu8 Te11 (Figure 14). This
compound has a Cu/Te framework with large tunnels running
y parallel to b-axis, which are filled with K+ ions. This
framework is assembled from fused and linked [Cu8 Te12 ]
z
x clusters. A3 Cu8 Te10 is mixed valence compound and exhibits
metallic properties, whereas K4 Cu8 Te11 and A2 BaCu8 Te10 are
narrow band-gap semiconductors.
Figure 13 The layered structure of A2 BaCu8 Te10 . The [Cu8 Te12 ]
The K2 Cu2 Te5 forms under solventothermal conditions.63
pentagonal dodecahedral cage-cluster with Ba atoms inside. The Te
atoms are open circles. Cu atoms are small black circles It contains a three-dimensional framework with the primary
z
y
(a)
x
y
(b)
Figure 15 (a) The structure of K2 Cu2 Te5 with the K atoms omitted.
(b) The Cu2 (Te3 ) layers (indicated in the shaded boxed area in (a))
Figure 14 The tunnel framework structure of K4 Cu8 Te11 . The Te showing the linking modes of the Te3 2 units. The Te atoms are open
atoms are open circles. Cu atoms are small black circles circles. Cu atoms are small black circles
CHALCOGENIDES: SOLID-STATE CHEMISTRY 9
(a) (b)
Figure 18 The structure of (a) Rb4 Au6 S5 and (b) Cs4 Au6 S5
respectively, are filled with Na+ cations, while two smaller Figure 20 The framework structure of K2 Cd2 S3
channels (stacks of Cd2 S2 and Cd3 S3 rings) are devoid of
Na+ (Figure 21). Na6 Cd7 S10 is a semiconductor with a room
temperature band gap of 2.62 eV. compounds have been compared with those of the three-
The isomorphous, layered A2 Cd3 S4 , A2 Cd3 Se4 ,(A = K, dimensional binary parent phases CdS, CdSe, and CdTe,
Rb) and K2 Cd3 Te4 feature (Cd3 Q4 )n 2n layers separated as well as those of the nanometer-sized CdQ clusters. A
with A+ cations. The layers are composed of (Cd3 Q4 )2 conceptual context has been presented to connect all these
units shaped as truncated cubes (Figure 22). The compounds different ternary and binary compounds as shown in Figure 23:
are semiconductors with energy band gaps of 2.75, 2.92, A layered mercury telluride, Rb2 Hg3 Te4 , was discovered
2.36, 2.37, and 2.26 eV respectively and also display strong during an exploration of hydro(solvo)thermal synthesis of
photoluminescence. The structure and properties of these tellurides at temperatures somewhat above the boiling
CHALCOGENIDES: SOLID-STATE CHEMISTRY 11
6
S
S
Cd
S
S
Molecular 0-D "0-Dimensional" Linear chain Layered 2-D Channeled 3-D Dense 3-D
compound CdQ clusters compound compound compound compound
Conduction
LUMO
band
Eg Eg Eg Eg
Eg
Valence
band
HOMO
Figure 23 Structural evolution to lower dimensional structures in a A2 Q/MQ systems with increasing A2 Q/MQ ratio. The most dense and
highest dimensionality exists in the MQ itself and the least in the compound that forms with the highest possible A2 Q/MQ ratio giving
molecular [MQn ]z species
12 CHALCOGENIDES: SOLID-STATE CHEMISTRY
o a
b Te(2)
Te(1)
Te(1)
Hg(1)
Hg(2)
Te(2)
Rb
x
z
y
c
A fascinating ternary compound is Cs2 Sn3 S7 1/2S8 , Bismuth chalcogenide compounds have been investigated
which was synthesized by reacting Sn with a Cs2 Sx extensively because of their relevance as thermoelectric
flux at temperatures from 400 500 C.88 Cs2 Sn3 S7 1/2S8 materials. As a result a large variety of them was
encapsulates S8 molecules in much the same way Cs3 Te22 discovered and shown to posses a fascinating array of
encapsulates Te8 molecules. The structure has an extended structural arrangements. Some interesting phases are KBi3 S5 ,
framework of [Sn3 S7 ]2 anionic layers which possess large RbBi3 Se5 ,93 KBi6.33 S10 ,94 K2 Bi8 Q13 (Q = S, Se)95 and
open rings (Figure 27). As these layers stack along the c Cs3 Bi7 Se12 .96 These compounds belong to the general family
direction, the large open rings are aligned forming channels. of compounds (A2 Q)n (Bi2 Q3 )m (A = alkali metal; Q = S, Se).
Cs+ cations are located between the layers and S8 molecules Structurally, they can be thought of as an intimate composite
are found to occupy the space within the channels and also of two different structure types interconnected to form a 3D
interacting with the Cs+ cations. The [Sn3 S7 ]2 layer has network. They have three-dimensional structures made up of
been crystallized with a number of other counterions but modular fragments that connect to form tunnels filled with
none of these analogs encapsulates sulfur or other neutral K+ cations.
molecules.89,90 In addition, several selenium analogs are also The [Bi6.33 S10 ] framework is made of edge-sharing BiS6
known.91 octahedra in a structure that is very similar to that of the
An interesting example of a compound is Cs2 SnTe4 mineral cosalite (Pb2 Bi2 S5 ) (Figure 28). A key feature of this
prepared by the methanolothermal reaction of Cs2 CO3 with Sn and other structures of this type is the occurrence of mixed
and Te at 190 C,92 The crystal structure contains chain anions occupancy sites between K and Bi in the structures. The mixed
[SnTe4 ]2 in which individual SnTe4 tetrahedra are linked via occupancy between nonisoelectronic elements can influence
TeTe bonds of length 2.814(3) A. Weak Te Te secondary the electrical properties of these materials. These sites tend to
bonds of length 3.631(3) 3.663(3) A connect neighboring be the high coordination sites (coordination number >6). The
chains into a framework structure. Nine Te atoms from structure of K2 Bi8 S13 is a three-dimensional assembly made
three chain anions participate in the coordination sphere of up of Bi2 Te3 -, NaCl-, and CdI2 -type infinite rod shaped blocks
the cesium cation. Apparently, the highly basic environment (Figure 29(a)).
created by the presence of [CO3 ]2 ions resulted in excess K2 Bi8 Se13 comes in two modifications - and - in two
polytelluride ions most likely via a disproportionation reaction structure types and represents an example where similar
of elemental Te. building blocks combine to give compounds with the
same stoichiometry but different architecture.97 -K2 Bi8 Se13
consists of Bi2 Te3 -, CdI2 -, and Sb2 Se3 -type rod fragments. -
K2 Bi8 Se13 is isostructural to K2 Bi8 S13 . Overall, the structure
of -K2 Bi8 Se13 is slightly denser, because in the latter 25% of
the Bi atoms are found in a trigonal pyramidal geometry,
while in the former all Bi atoms are in an octahedral
or higher coordination geometry (see Figure 29(b)). Other
related compounds include, K2.5 Bi8.5 Se14 , Rb2 Bi8 Se13 ,98
K1+x M42x M7+x Se15 (A = K, Rb; M = Pb, Sn; M = Bi,
Sb),99 and so on.100
Bi2Te3 type
NaCl type
Bi2Te3 type
CdI2 type
CdI2 type
Sb2Se3 type
Bi9/K1 Bi8/K3
Z Y
X X
(a) (b)
Figure 29 (a) The structure of -K2 Bi8 Se13 . (b) The structure of -K2 Bi8 Se13 . The modular fragments of the structure are related to the
Bi2 Te3 and CdI2 structures are shown
Cs3 Bi7 Se12 is a fascinating example of a layered compound Cs atoms present in Cs3 Bi7 Se12 and because of all the void
which undergoes stepwise redox-induced oxidative coupling space now created they show a rather diffuse character (i.e.
of its layers to convert to a three-dimensional structure. high temperature factors).
It is capable of two successive, single crystal to single A rather unusual compound is BaBiTe3 , which is in fact
crystal oxidative transformations. These processes convert the a polytelluride (i.e. contains Te Te bonds).101 Its structure
original 2D framework to another 2D framework and finally is layered with [BiTe3 ]2 slabs alternating with Ba cations
to a 3D framework. Well-defined solid-state processes of this (Figure 31). The presence of TeTe bonds form zigzag Te
type, besides being spectacular, are of fundamental importance chains arranged in ribbons. The flat Te ribbons alternate
in chemistry because they could provide basic systems for between NaCl-type BiTe blocks.
mechanistic studies. Cs3 Bi7 Se12 has a layered structure made Finally, the layered anisotropic phase CsBi4 Te6 has been of
of Bi2 Te3 -type blocks (Figure 30(a)). A key characteristic interest because of its enhanced thermoelectric properties. Its
of the structure is that adjacent slabs come in close, structure is composed of anionic [Bi4 Te6 ] layers alternating
nonbonding contact by rows of Se(4) atoms. Cs3 Bi7 Se12 can with layers of Cs+ ions (see Figure 32).102104 The average
be oxidized topotactically to give Cs2 Bi7 Se12 (Figure 30(b)). oxidation state of Bi is less than three with some of the Bi
Remarkably, Cs2 Bi7 Se12 also oxidizes topotactically to give atoms forming BiBi bonds. The presence of such bonds is
CsBi7 Se12 (Figure 30(c)). The structure has essentially the very unusual in bismuth chalcogenide chemistry and it is not
same [Bi7 Se12 ]3 framework only now the original layers are clear at the moment whether they play a role in the enhanced
all linked with a new set of Se(4)-Se(4) bonds forming a truly thermoelectric properties of the material. The Bi coordination
3D framework. The Se2 2 groups act as the pillars between geometry is octahedral. This material has strong anisotropic
the original layers. CsBi7 Se12 contains only 1/3 of the original electrical transport and thermal transport properties.
CHALCOGENIDES: SOLID-STATE CHEMISTRY 15
Close contact
of Se(4) atoms
Bi2Te3-type
Cs1
Cs2
a
c
(a)
Figure 31 The layered structure of BaBiTe3 . Te atoms are in
open circles
Se4
z Bi
Te
Cs
x
y
(a)
Figure 38 The LaCuS2 structure-type in two perspectives. On the left the Cu atoms were omitted to highlight the LaS2 framework. Large
black spheres represent RE, intermediate-size black spheres represent M, and small black spheres represent Q atoms. The unit cell is outlined
here and in most succeeding figures
Z
x
X y
Figure 39 YCuS2 structure. Open circles are S atoms and small Figure 40 View of the structure of ErAgSe2 along the c-axis
black circles are Cu atoms
Zr i
Zr o Zr i
The compounds Sc6 AgTe2 , Sc6 Cu0.80 Te2.20 and Sc6 CdTe2 ,
have similar stoichiometry to those described above but
possess a different structural motif,128 that is, isotypic with
Sc6 PdTe2 . The structure can be viewed as heterometal
sheets lying parallel to the b-c planes that are separated
by isolated tellurium atoms. These sheets can also be
viewed as a polymerization of two different types of metal
chains in Sc2 Te (blades and zigzag chains) by heterometal
(M) replacements of some intervening tellurium atoms, The
new Sc6 CuTe2 and Sc6 AgTe2 are isostructural with Sc6 PdTe2 .
The Sc6 AgTe2 structure viewed along the short b-axis is given
in Figure 46. The structure can be described as the result of a
polymerization of two kinds of scandium metal chains, which
were formerly described in Sc2 Te (see above) as separate
double octahedral chains or blades (blue) and zigzag chains
b
(black), via displacement of the Te1 atom by a strongly
a
bonding heterometal Ag, and so on. The resulting condensed
heterometal sheets are separated by isolated Te atoms (red)
along the a-axis.
Figure 44 Approximate (001) projection of the Zr6 FeTe2 struc- Er7 Ni2 Te2 is the most metal-rich of the ternary rare earth
tures. The zirconium, iron, and tellurium atoms are shown as chalcogenides. The structure is shown in Figure 47. The basic
cross-hatched, hatched, and open circles, respectively. Bonds shown structural unit is a distorted, Ni-centered, tricapped trigonal
indicate the ZrZr and ZrFe contacts prism of Er that is fused with similar prisms by sharing the
Er3 triangular bases to form an infinite 1 [(Er3 Er3/2 Er3/2 )Ni]
chain that propagates along the b-axis. These infinite chains
are condensed to form corrugated layers across the bc plane
by sharing Er zigzag chains, which are composed of capping
Figure 45 Projection of the Zr6 Fe1x Q2+x (Q = S, Se) structures Figure 46 Unit cell of Sc6 AgTe2 . The blue atoms are Sc in the
down the [001] direction. Zirconium, iron, and chalcogen atoms blade unit, the dark atoms are Sc4 that form the zigzag chains, the
are shown as cross-hatched, hatched, and open circles, respectively. yellow atoms are silver, and red atoms are tellurium. The structure is
Bonds shown indicate the ZrZr and ZrFe contacts infinite along the view direction
CHALCOGENIDES: SOLID-STATE CHEMISTRY 21
1
(a) Zr6CoAl2
(b) Hf5FeTe3
(c) Er7Ni2Te2
(d) Zr3Fe
Figure 47 The Er7 Ni2 Te2 structure. Er and Ni atoms are shown as Figure 48 Arrangements of trigonal prismatic building blocks into
dark circles with and without bonds, respectively. Te atoms are open (a) single chains in the Zr6 CoAl2 structure, (b) double chains in
circles. ErTe and ErNi bonds are not shown for clarity. Circled the Hf5 FeTe3 structure, (c) layers in the Er7 Ni2 Te2 structure, and
regions 1 and 2 are depicted below (d) a 3-D network in the Zr3 Fe structure. Early transition metals are
shown as larger circles, and late transition metals are smaller. Some
metal metal bonds are omitted for clarity
Er atoms on one TTP and inner Er on the adjacent TTP (see
region 1 in Figure 47). Finally, vertex condensation forms
links between individual layers that result in the overall
The Sc14 M3 Te8 (M = Ru, Os) phases represent yet another
structure (see region 2 in Figure 47). Tellurium atoms reside
structure-type among metal-rich ternary chalcogenides. In this
between the metal metal bonded layers, on bc-planes.
motif, scandium atoms define infinite chains of alternate trans-
There is a structural relationship between Er7 Ni2 Te2
face-sharing cubes and pairs of square antiprisms in which
and three other structures: Zr6 CoAl2 -type (e.g. Zr6 MTe2 ,
Sc6 MTe2 , Gd6 MTe2 ), Hf5 FeTe3 , and Zr3 Fe. All can be each polyhedron is also centered by an M atom (M = Ru, Os).
constructed using centered transition metal trigonal prisms as These chains are further linked into a three-dimensional (3D)
fundamental building blocks, but with different condensation structure by Sc(Te2 Te4/2 ) octahedra through strong ScTe
schemes (Figure 48). In the Zr6 CoAl2 -type structure, bonding interactions. A projection of the Sc14 Ru3 Te8 structure is shown
between the capping and apical atoms of adjacent trigonal in Figure 49. Scandium metal plays two roles: one as Sc3
prisms interconnects single trigonal prismatic columns. In in chains of individual octahedral complexes [Sc(Te2 Te4/2 )]
Hf5 FeTe3 , double chains are formed by edge condensation of centered at 1 /2 , 0, z, and so on. The second role is seen in a side
single chains, and the double chains are then stitched together view in Figure 50 where Sc atoms define infinite columns of
into a 3D network by forming longer bonds between the confacial clusters, each centered by a Ru or Os atom. In these
capping atoms not involved in condensation. Formation of columns, are found square antiprismatic units that share faces.
condensed intermetallic layers becomes characteristic in the Each metal unit is connected to four Te-rich bridging chains
Er7 Ni2 Te2 structure. Successive layers are shifted relative to built of Sc(3)Te6 octahedra to complete the 3D structure. The
one another along the c direction and are linked together by Te atoms have trigonal prismatic and pentagonal bipyramidal
sharing capping atoms such that Te atoms are accommodated configurations, respectively. Physical property measurements
at two chemically inequivalent sites between the layers. A show that Sc14 Ru3 Te8 is metallic and Pauli-paramagnetic,
similar but more symmetrical layer architecture exists in consistent with the results of extended Huckel band structure
Zr3 Fe, which in turn is a hexagonal-close-packing example calculations. The ScM and ScTe interactions are major.
in metals. Adjacent layers in the Zr3 Fe structure stack The presence of early transition metals or rare earth
vertically, sharing one Zr atom in every trigonal prismatic elements is not necessary for the stabilization of metal-
unit. This 3D network is even more condensed owing to rich compounds. This is shown by the metal-rich nickel tin
the formation of extensive ZrZr bonds between the layers sulfides Ni6 SnS2 and Ni9 Sn2 S2 , which were found during
(Figure 48(d)). investigations of phase relations in the ternary NiSnS
22 CHALCOGENIDES: SOLID-STATE CHEMISTRY
SC2 SC2
SC1 TE1 SC1
TE1
SC1 TE2 SC1
SC2 SC2
SC2 SC1
TE2 TE2
TE1 TE1
TE1 SC1 TE1
SC2
SC2
TE1 SC1 TE1
TE1 TE1
TE2 SC1 TE2
SC2
SC2 SC2
SC1 TE1 SC1
TE1
SC1 TE2 SC1
SC2 SC2
Figure 49 Projection of the unit cell of Sc13.2 Ru3 Te8 . The confacial Sc-based cubes and antiprisms centered by Ru are clearly seen. Sc3
atoms center infinite chains of edge-sharing {ScTe6 }n octahedra
Sc1 Sc1
Sc2 Sc2 Sc2
3.28 3.41 Sc2 Sc2
3.3
3
3.25
2.7
6
9
2.7
3.20
2.6
Sc3
Te2
Te1 Te1
Figure 50 Segment of condensed {Sc4 Ru}n infinite chain of trans-face-sharing cubic (Sc1) and square antiprismatic (Sc1 and Sc2) polyhedra
centered by Ru1 and Ru2, respectively. Distances are in A
CHALCOGENIDES: SOLID-STATE CHEMISTRY 23
Figure 52 (a) The MQ and TQ2 parts of a misfit layer compound. (b) Different stacking motifs between the so-called quadratic and
hexagonal slabs
24 CHALCOGENIDES: SOLID-STATE CHEMISTRY
4 QUATERNARY COMPOUNDS
Q(2)
Q(1)a
M Ma
C
Q(1) Q(1)b
Q(2)a Q(2)b
Cu Cua
Q(1)c
Mb
A O B
Cu
O B
A
Figure 55 (a) View perpendicular to a single anionic layer of the ACuMQ3 structure-type. (b) The ACuMQ3 structure-type (A = Cs,
M = Ce, Q = S; or A = K, M = U, Q = Se) as seen down the a-axis, parallel to the anionic layers (circles with nonshaded octants, A; large
open circles, Cu; small open circles, M; circles with shaded octants, Q)
(a) (b)
Figure 58 Striking difference between (a) the structure of the square Te-net determined by conventional crystallography (average tetragonal
structure) which predicts a metallic compound and (b) the structure of the incommensurately modulated Te-net determined by higher
dimensional crystallography. Two motifs are observed: Te groups with a V shape and Te groups with a W shape. Occasionally, as the motif
changes from V to W, the lone Te atom (black dots) found between two W motifs is at a distance slightly shorter than 3.1 A of a W motif (one
such example is observed in the figure). This structure explains the narrow band gap semiconductor behavior of this compound
K layer
Te square net
CeTe3
layer
Te square net
K2.4Ag4.5Te3
layer
Figure 59 The structure of K2.5 Ag4.5 Ce2 Te9 and representative electron diffraction pattern with the e-beam perpendicular to the square
Te-net. The weak supercell spots appear between the strong subcell reflections
emergence of the molten polychalcogenide flux methodology materials. In many cases, the compounds stabilized under
in the exploratory synthesis of complex chalcogenides. polychalcogenide flux conditions are only kinetically stable
This approach to new chalcogenides has been developed and cannot be synthesized at higher temperatures. Lower
and brought to the main stream of inorganic chemistry temperatures, coupled with the presence of a liquid,
methodology mainly in our laboratories. This method also make possible the use of molecular assemblies as
of synthesis and exploration has simplified access to building blocks for incorporation into solid-state structures,
low and intermediate temperatures (160 600 C) and and consequently the construction of complex multinary
contributed to the discovery of some very interesting solids.
CHALCOGENIDES: SOLID-STATE CHEMISTRY 29
An excellent way to search for new solid-state materials about chalcophosphates, develop their syntheses and explore
is the use of molten salts as solvents in which to carry out their properties.
exploratory synthetic reactions. For the discovery of chalco-
genide materials, the use of alkali metal polychalcogenides, of
the type A2 Qx (A = alkali metal, Q = chalcogenide) as sol- 4.2.1 Chalcometallate Salts
vents, is very appropriate as we and others have demonstrated By chalcometallate compounds we mean those that are
already. As solvents for intermediate temperature reactions, based on complex anions of the type [Mx Qy ]z where M is a
A2 Qx salts are especially well-suited because the melting high oxidation state metal or metalloid and Q is a chalcogen.
points range between the extremes of K2 S at about 850 C The most well-known chalcometallate anions are [PQ4 ]3 ,
to K2 S4 at 145 C, with the majority of compositions melt- [P2 Q6 ]4 , [GeQ4 ]4 , [SnQ4 ]4 , [AsQ3 ]3 , and [SbQ3 ]3 ,
ing at < 300 C. The polytelluride versions melt between but a large variety of others also exist. These anions can
300 500 C. Low melting, A2 Qx fluxes remain nonvolatile be regarded as building blocks for constructing ternary and
over a wide temperature range, and so once above the melt- quaternary chalcogenide frameworks. They can form in situ
ing point, reaction temperatures can be varied considerably during synthesis or be introduced in the reaction as their alkali
without concern for solvent loss. Polychalcogenide fluxes are metal salts. When combined with various metal cations, these
highly reactive towards metals because they are very strong anions can lead to an astonishing variety of compositions and
oxidants. Reactions between metals and molten A2 Qx are structural arrangements.
performed in situ. A convenient way to stabilize these anions and make
The polychalcogenide salts can be made by allowing them available for reaction is through a flux methodology.
stoichiometric amounts of elemental chalcogenide to react This approach to new metal chalcogenides has simplified
an with alkali metal in liquid NH3 at 70 C or by direct access to low and intermediate temperatures (160 600 C)
combination reactions between the alkali metal and the and contributed to the discovery of many fascinating solid-
chalcogen. In the latter case, care must be taken to avoid state materials. Lower temperatures, coupled with the presence
explosions owing to the highly exothermic nature of the of a flux, also make possible the use of molecular assemblies
reaction. To synthesize new compounds, one or more metals as building blocks for incorporation into solid-state structures.
are added directly to the A2 Qx /Q reaction mixture and heated When using the flux approach, the best way to generate
in a sealed Pyrex or quartz container. Crystalline products chalcometallate anions such as [PQ4 ]3 , [P2 Q6 ]4 , [GeQ4 ]4 ,
either precipitate from the melt or form on slow cooling [SnQ4 ]4 , [AsQ3 ]3 , and [SbQ3 ]3 is to introduce P, Ge, Sn,
of the melt, depending on the specific stoichiometric and As, or Sb in the appropriate amount into the A2 Qx melt. For
example, the polychalcophosphate fluxes form by simple in
processing conditions. Presumably, the nucleated species are
situ fusion of A2 Q/P2 Q5 /Q, (Q = S, Se) (see equation (2)).
in equilibrium with the soluble intermediates, especially if the
The acid/base characteristics of the Ax [Py Qz ] fluxes are very
flux is present in excess, and hence a solvation/reprecipitation
different from those of A2 Qx fluxes in that they tend to
effect (often referred to as the mineralizer effect) occurs. This
be more basic. The relatively good solubility properties of
aids in the growth of high quality single crystals because the
Ax [Py Qz ] salts in water and polar organic solvents allow for
flux can redissolve small or poorly formed crystallites and then
easy isolation of products.
reprecipitate the species onto larger, well-formed crystals. The
advantage of the flux method is that one allows the system to x y T > 300 C
end up where it wants in the kinetic or thermodynamic sense A2 Q + P2 Q5 + zQ Ax [Py Qx+y+z ]
2 2
without attempting to force upon it a certain stoichiometry or (A = alkali metal) (2)
structure. Provided the temperature and time are appropriate,
the reaction system has all the ingredients to form a new In these melts, various [Py Qz ]n species are solubilized in
phase. The benefit of this becomes apparent from the unsual excess polychalcogenide flux. The melting points of Ax Py Qz
compositions often found for the new materials which most are in the intermediate temperature range 300 400 C, making
certainly could not have been predicted a priori. possible the synthesis of even metastable phases. The existence
Chalcophosphates are compounds that contain phosphorus of various [Py Qz ]n species in the melt is influenced by the
and chalcogen atoms in which phosphorus is oxidized and Ax Py Qz composition. Their exact distribution as a function
there exists at least one PQ bond, where Q = S or Se. To date, of composition, however, is not well-known; however, one
there are no examples with Q = Te. There exists a wonderful can reasonably speculate the equilibria shown in Figure 60.
structural diversity among these compounds due primarily to Recognizing that there are such equilibria that can be
the various [Py Qz ]n building blocks that can be stabilized controlled is important because flux composition determines
and their fascinating variety of binding modes. In addition to the product outcome. Similar considerations apply for the
their rich structural chemistry, several of these phases possess [GeQ4 ]4 , [SnQ4 ]4 , [AsQ3 ]3 , and [SbQ3 ]3 anions.
interesting ion-exchange, intercalation, magnetic, electrical, Although early investigations concentrated on the reactivity
and optical properties. Therefore, it is important to inquire of Bi, almost all elements have good reactivity in them, as
30 CHALCOGENIDES: SOLID-STATE CHEMISTRY
Q Q 3
Q P
+Q Q
4 Q 3 Q
Q Q
Q Q 4
Q
+2Q2 2 Q P
P P
Q PH
Q Q Q P
Q Q Q Q
Q
Q
Oxidative
coupling 4
Q
Q
P Q
P
Q Q
Q Q
Q
Figure 60 Possible chalcophosphate anion equilibria present in alkali metal polychalcogenide fluxes
Sb1 Se6
Se5
P1
Se1
Se2 Se3
P2
a 0 Se4 K1 b
Figure 61 View of -KSbP2 Se6 perpendicular to the screw axis. The weak interchain bond is emphasized with a dashed line
has been demonstrated for a large fraction of the metallic The new quaternary niobium thiophosphates ANb2 P2 S12
elements. Many quaternary chalcophosphate compounds (A = K, Rb, Cs) form by allowing Nb metal, A2 S, P2 S5 , and
have been generated in this fashion including ABiP2 S7 S to react at 600 700 C. They crystallize as stuffed variants
(A = K, Rb),167 A3 M(PS4 )2 (A = K, Rb, Cs; M = Sb, of the tetragonal TaPS6 structure-type. Their structures
Bi),168 Cs3 Bi2 (PS4 )3 , and Na0.16 Bi1.28 P2 S6 , -, -KMP2 Se6 are based on double helices formed from interpenetrating,
(M = Sb, Bi),169 A2 MP2 Se6 (A = K, Rb, Cs; M = Pd, Zn, Cd, noninteracting spiral chains of binuclear [Nb2 S12 ] cluster
Hg),170 APdPS4 ,(A = Na, K, Rb),171 K2 PdP2 S6 ,172 Cs2 PdP2 units and [PS4 ] thiophosphate groups. The cavities and
Se6 ,172 Rb8 Hg4 (Se2 )2 (PSe4 ),173 TI2 AuPS4 ,173 KAu5 P2 S8 ,174 tunnels, which are formed by the helical chains, are filled
K4 In2 (PSe5 )2 (P2 Se6 ),175 Rb4 Ti2 (P2 Se7 )(P2 Se9 )2 ,176 Na1.5 - with A+ ions. Temperature-dependent conductivity studies
Pb0.75 PSe4 , K3 RuP5 Se10 ,177 K3 Cu3 P3 Se9 ,178 Cs2 CuP3 S9 ,179 reveal thermally activated electrical transport behavior.
KInP2 Se6 ,180 NaCrP2 S6 , ANb2 P2 S12 (A = K, Rb, Cs),181 ANb2 P2 S12 may be considered a chalcogenide analogue of
K2 AuPS4 182 and A2 AuP2 Se6 (A = K, Rb).182 metal phosphate bronzes.
CHALCOGENIDES: SOLID-STATE CHEMISTRY 31
Li
Se1
Se3
P Eu
Se2
a b
(a)
Se1
K
P
Se3
Eu
Se2
b
a
(b) c
Figure 63 (a) The structure of LiEuPSe4 viewed down the a-axis with thermal vibrational (80%) ellipsoids. This view shows the 1 [EuPSe4 ]
framework that creates tunnels for the Li ions to reside. (b) The structure of KEuPSe4
CHALCOGENIDES: SOLID-STATE CHEMISTRY 33
Se Se
Ge Se
(a) Se Se
a
c
(a) b
[Hg2Ge2S8] layer
b a
Linear Hg
(b)
(b)
framework can be viewed as slabs of [Hg2 Ge2 S8 ]4 linked in the chain is a centrosymmetric [Sn(AsS2 (S2 ))]2 dimeric core
by linear Hg(1) atoms. There are two types of Hg2+ atoms, that propagates down the chain with bridging 2 -S2 ions.
a highly distorted tetrahedral [Hg(2) seesaw-shaped HgS4 ] The pyramidal -[AsS4 ]3 anion features the As3+ ion and
and a linearly coordinated Hg(1) atom. The -form is similar a disulfide unit, and it is very different from the well-known
but it differs in how the linear Hg atoms link the [Hg2 Ge2 S8 ]4 As5+ species -[AsS4 ]3 . All three terminal sulfur atoms are
slabs (Figure 65). involved in binding the two Sn4+ ions. The terminal atom, S(1),
The compounds K2 EuSiSe5 , K2 EuGeSe5 are isostructural of the disulfide group serves to bridge the Sn atoms in the core
and they have a layered structure in which 9-coordinate (Figure 67(b)). This pyramidal unit is to be contrasted with
Eu(II) atoms are linked into a layer by (GeSe5 )4 units. The the highly symmetrical tetrahedral -[AsS4 ]3 anion, which is
(GeSe5 )4 unit, shown in Figure 66(a), is a Ge(IV) tetrahedron formally an As5+ species and isostructural to the more familiar
with one of its arms being a diselenide (Se2 )2 unit. It is [PS4 ]3 anion. Therefore, we see here a drastic departure of
isoelectronic to the [PSe5 ]3 unit observed in thiophosphate the thioarsenate flux chemistry from that of the thiophosphate
chemistry. Five different (GeSe5 )4 units are coordinated to which is attributed to the electronegativity difference in the
each europium atom. Two units are bound to europium with two elements. It is possible that the two isomers are in fact
one selenium atom, two units are bound with two selenium in equilibrium with each other. Presumably, this equilibrium
atoms, and the fifth (GeSe5 )4 unit is bound to europium with would be sensitive to the basicity of the flux which to a large
three of its selenium atoms. Each (GeSe5 )4 unit links four extent is controlled by the formal K2 S/As2 S3 /S ratio, and by
different Eu2+ atoms within a layer as seen in Figure 66(b). the nature of the alkali ion. Thus, by controlling such equilibria
A classical example of reactivity of main group metal in in the flux, one could favor different thioarsenate anions to
thioarsenate melts and how Lewis flux basicity affects the produce different outcomes.
chemistry is that of Sn. Low Lewis basicity fluxes favor the The K2 SnAs2 S6 compound is trigonal with layers
formation of KSnAsS5 , and as the basicity increases (e.g. by consisting of SnS6 octahedra and [AsS3 ]3 pyramids
adding more K2 S) the reaction lead to layered K2 SnAs2 S6 (Figure 68). The layers are separated by seven coordinate
instead.210 The former compound has infinite chains and the K+ ions. Topologically, the structure is TiS2 -type with Sn4+
rare pyramidal -[AsS4 ]3 ligand (Figure 67(a)). The key unit cations in the octahedral Ti positions and [AsS3 ]3 anions at
a
c
(a)
Sn
S1
S4
(b)
As S3
Figure 67 (a) The structure of KSnAsS5 looking down the c-axis (b) A single chain of KSnAsS5
CHALCOGENIDES: SOLID-STATE CHEMISTRY 35
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Acknowledgment
191. J. A. Aitken, K. Chondroudis, V. G. Young, and M. G.
Kanatzidis, Inorg. Chem., 2000, 39, 1525. I thank Dr. Alain Meerschaut for providing material regarding
192. J. A. Aitken, M. Evain, L. Iordanidis, and M. G. Kanatzidis, the misfit compounds. I also thank the National Science
Inorg. Chem., 2002, 41, 180. Foundation for generous support.
Chlorine, Bromine, Iodine, the halogens form a remarkable homologous series, certain
discontinuities are evident. Principal among these is the
& Astatine: Inorganic exceptional nature of fluorine and its chemically reactive
compounds. It has, therefore, become customary to separate
Chemistry the discussion of fluorine chemistry from the rest of the
halogens and treat this as a separate subject.
Jian-Ping Lang
Suzhou University, Suzhou, China
2 ATOMIC STRUCTURE
Based in part on the article Chlorine, Bromine, Iodine, & Astatine:
Inorganic Chemistry by Jacob Shamir which appeared in the
Encyclopedia of Inorganic Chemistry, First Edition. Some atomic properties are summarized in Table 1 and
these are further discussed in the sections that follow.
1 Introduction 1
2 Atomic Structure 1
3 Molecular Properties 2 2.1 Electronic Configuration
4 Halogen Compounds 5
The electronic configuration of the halogen atoms in
5 Interhalogen Compounds 6
their ground state is ns2 np5 , just one electron short of
6 Hydrogen Halides 12
7 Halogen Oxides 13
the corresponding noble gas electronic configuration with
8 Organic Polyvalent Halogen Derivatives 19 the so-called inert octet. This electronic structure makes
9 Related Articles 20 the halogens extremely powerful electron acceptors with
10 References 20 the highest electron affinities of all atomic elements (see
Electron Affinity). Consequently, the ionization potentials of
the halogens are the highest known, except for the noble
gases (see Ionization Potential). As a result, the dominant
feature of the halogens is the ease with which their atoms
accept an electron, forming either a uninegative anion X , or
1 INTRODUCTION a single covalent bond X. The compounds formed therefore
range from ionic salts at one extreme to covalent molecules at
The elements of group 17, fluorine, chlorine, bromine, the other.
iodine, and astatine, are collectively called the halogens and In addition to the possibility of forming monoatomic anions
these are the most representative nonmetals in the periodic at the 1 valency state or monovalent covalent bonds, the
table (see Periodic Table: Trends in the Properties of the halogens can also form bridges between two other atoms, in
Elements). The nonmetallic feature is indicated by the high a manner similar to hydrogen bonding, through the formation
value of the ionization potentials of the halogens, which are of covalent bonds with the two-bridged atoms. Many halogen
only 1 4 eV lower than those of the corresponding noble gas compounds exist, in which the central halogen has a formal
atoms. As a result, the halogens are extremely electronegative oxidation state of +1, +3, +5, and +7, as in the oxyhalogen
with strong electron affinities. Many general references are species, and some cationic species are also known.
available and we list only a few.14 The name halogen, based
on a Greek word, is intended to describe the ability of these
elements to combine directly with metals to form salts. 2.2 Stable Isotopes
The diatomic nature of the elemental halogens clearly
indicates their nonmetallic nature. Only hydrogen, nitrogen, Several chlorine isotopes exist with mass numbers ranging
and oxygen share this property under normal conditions. The between 32 and 40. The two stable isotopes are 35 Cl and 37 Cl
increase of the boiling points, melting points, and volatility of with natural abundances of 75.77% and 24.23% respectively,
the halogens are compatible with the increase in the van der while the others are radioactive. Bromine also has two stable
Waals forces with advancing size and Polarizability of the isotopes, 79 Br and 81 Br, with natural abundances of 50.69%
atoms and molecules. and 49.31% respectively, while the others are radioactive.
Everyday uses of halogens or their compounds are well Iodine has only one stable isotope, 127 I, and numerous
known, such as the use of chlorine in purifying drinking water, radioactive ones are known. Astatine is known only as its
the use of iodine as an antiseptic, and the use of bromine in radioisotope (see Radioactive Decay).
photographic films as the compound silver bromide. Radioisotopes of the halogens have found uses in studies of
The title of this article includes all the halogens except the exchange reactions and reaction mechanisms. A radioactive
first: fluorine (see Fluorine: Inorganic Chemistry). Although iodine isotope is used in medical diagnostics.
2 CHLORINE, BROMINE, IODINE, & ASTATINE: INORGANIC CHEMISTRY
Table 1 Atomic properties of the halogens aqueous solutions of sodium chloride (equation 2), whereas
in the electrolysis of the molten NaCl salt, the coproduct
Property Cl Br I At is sodium metal, rather than sodium hydroxide. The old
Atomic number 17 35 53 85 Deacon process was based on the copper-catalyzed reaction
Atomic weight 35.453 79.904 126.9045 209.99 (equation 3). This has been made more efficient by passing
Ionization 1255.7 1142.7 1008.7 (926) HCl over CuO at 200 C to give CuCl2 and H2 O after which
energy
CuCl2 at 300 C is treated with O2 .
(kJ mol1 )
MnO2 + 4HX MnCl2 + X2 + 2H2 O (X = Cl, Br) (1)
2.3 Magnetic Moments Cl + H2 O OH + 1
2
Cl2 + 1
H
2 2
(2)
2HCl + 1
O
2 2
Cl2 + H2 O (3)
The fluorine atom has a nuclear spin number of 1/2,
similar to that of hydrogen, and is therefore suitable for NMR
measurements, giving narrow lines. The other halogens have The main uses of chlorine are the following: (1) the
nuclear spin numbers >1/2 (3/2 for chlorine and bromine, 5/2 production of chloro-organic compounds, such as vinyl
for iodine), and so are unsuitable for NMR studies. chloride and ethylene dichloride for the plastics industry,
as solvents, refrigerants, insecticides, and dyes (about 70%);
(2) as a bleaching agent of paper, pulp, and textiles, and
the disinfection of water supplies (about 20%); and (3) for
the production of a large variety of inorganic chemicals,
3 MOLECULAR PROPERTIES particularly covalent compounds.
Bromine can be obtained by oxidation of HBr with
3.1 Occurrence manganese dioxide (equation 1) or nitric acid. Industrially,
bromine is produced by oxidation of the bromide anion with
Chlorine was the first halogen to be isolated and sodium elemental Cl2 (equation 4). Elemental Br2 is then blown out
chloride, common salt, has been known from early times of the solution by passing steam or air through it. The vapor
as being essential to the human diet; as such it has been is then condensed or fixed chemically and finally purified.
mentioned in the Bible. Aqua regia, a mixture of hydrochloric
and nitric acids, has been known since the thirteenth century as 2Br + Cl2 Br2 + 2Cl (4)
a liquid for dissolving the very inert metal, gold. The ancient
color mentioned in the Bible as purple has been identified as The industrial use of bromine was dominated by the
a brominated organic compound, namely 6,6-dibromoindigo, production of ethylene dibromide as a valuable additive to
which used to be extracted from a small snail. gasoline to act as a scavenger for lead in the antiknock additive
Since the halogens are very reactive, they are never found tetraethyllead. Now that the use of Et4 Pb in gasoline has been
in nature as free elements. However, they are widespread and reduced, this consumption of bromine has also been reduced.
abundant in the form of salts, mostly containing the halide The pesticide industry uses large quantities of bromine, and an
anion. Large quantities of NaCl and KCl are found in pure increasing demand also exists in fire-retardant materials such
form as mineral deposits and can be mined directly. However, as fibers and wood. A well-known use of bromine is as AgBr
larger quantities are dissolved in water, as in oceans, inland in the photographic industry.
seas, lakes, and brines (e.g. the Great Salt Lake of Utah Iodine is produced by similar methods, namely, oxidation
and the Dead Sea in Israel). The liquid sources are usually of the iodide anion from brines by chlorine. However, iodine
concentrated by solar evaporation and the concentrated brines is also produced in a reductive process by reacting NaIO3 ,
are then processed to obtain the salts present. Iodine is found extracted from the natural source of Chilean saltpeter, with
in the sea as the iodide and also in Chile as an iodate salt, sodium hydrogen sulfite. The pentavalent iodine is reduced
IO3 . Chlorine is the 20th most abundant element in crystal to iodide (equation 5), which is then treated and oxidized
rocks, bromine the 46th, and iodine the 60th. with a sufficient amount of the mother liquor to liberate
elemental iodine (equation 5). In contrast to chlorine and
bromine, which have large industrial uses, iodine has no
3.2 Production and Uses predominant commercial use.
Chlorine can be obtained in the laboratory by oxidation
[IO3 ] + 3[HSO3 ] I + 3[HSO4 ] (5)
of HCl with a strong oxidizer such as manganese dioxide
+
(equation 1). The industrial production of chlorine is a major 5I + [IO3 ] + 6H 3I2 + 3H2 O (6)
section of the heavy chemical industry and is based on
electrolytic oxidation of the chloride anion. Chlorine, sodium The artificial radioactive element astatine is prepared by
hydroxide, and hydrogen are produced by the electrolysis of bombarding bismuth metal or bismuth oxide by particles,
CHLORINE, BROMINE, IODINE, & ASTATINE: INORGANIC CHEMISTRY 3
producing 20 isotopes. Among them, the longest-living species depending on the balance between six electrons in bonding
are 210 At (8.3 h) and 211 At (7.2 h). The astatine is separated orbitals (g2 u4 ) and four in antibonding orbitals (g4 ). This fits
from the bismuth source either by distillation or by extraction. a diamagnetic ground state with a bond order of unity.
In the first method, on the basis of the high volatility of The electronic spectra of the halogens arise from absorption
astatine, the reaction takes place in a current of nitrogen or in bands corresponding to the electronic transitions, in which an
vacuo, by heating the source to 300 600 C. The astatine is electron is excited from the antibonding g to the antibond-
then condensed on a cold surface. In the extraction process, ing u orbital (equation 6). The separation between these
the bismuth source is dissolved in perchloric acid containing two orbitals decreases as the atomic number of the halogen
some iodine that serves as a carrier of the astatine. The bismuth increases.
is then precipitated as a phosphate and the remaining liquid
can serve as an aqueous solution of astatine iodide, AtI. g2 u4 g4 g2 u4 g3 u1 (7)
I3 C12
C9 0(1)
C13 C8 0(3)
I(1)
N1 0(5) A)
C7 0(8) Rh(1) (1
Rh(2) 0(2) Rh
C1 C6
I2 I1
C2 C5 0(7) I(2) 0(4)
0(6)
C4
C3
Figure 1 A perspective view of the Zigzag conformation of the Figure 3 A view of the [Rh2 (O2 CCF3 )4 ]2 I2 . (Reproduced by
[(aridineI2 )2 ]I2 dimer. (Reproduced by permission of Wiley-VCH) permission of Wiley-VCH)
CHLORINE, BROMINE, IODINE, & ASTATINE: INORGANIC CHEMISTRY 5
Cl, Br) with dibromine gave rise to the platinum(IV) 4.2 Covalent Halides
salts [NBu4 ]2 [Pt2 Br10 ](Br2 )7 and [NBu4 ]2 [PtBr4 Cl2 ](Br2 )6 ,
which in the solid state form a polymeric network of Covalent halides can be prepared by various synthetic
bromine bromine interactions.12 routes. The simplest are direct reactions of elemental halogens
The relative acceptor strengths of the halogens and diatomic (equation 9), or hydrogen halides with elements (equation 10)
interhalogens to a given donor is: ICl > BrCl > IBr > I2 > or oxides (equation 11). In other processes, the oxides are
Br2 > Cl2 . Similarly, the donor capacity to a given halogen is: reacted with a halogen halide in the presence of carbon
benzene < polyalkylbenzenes alkyl iodides alcohols to combine with the oxygen (equation 12) or other reactive
ethers ketones < organic sulfides < organic selenides < carbon halides (equation 13). Exchange of halogens can also
amines. Many organic halogenation reactions are explained take place (equations 14 16). Anhydrous halides can also
on the basis of the presence of intermediates of halogen be obtained by dehydration of metal halide hydrates, using
charge-transfer complexes. reactants such as thionyl halide, which react with the hydrated
water (equation 17).
A majority of the halides of the pretransition metals in In general, with the same central atom, the covalency of
groups 1 and 2 of the periodic table, as well as those of the corresponding halides will decrease with a decreasing
the lanthanides and actinides at the valence states of +2 and halogen mass, namely, MIn > MBrn > MCln , as a result of
+3, are usually ionic compounds, whereas the nonmetals and the decrease of the polarizability, which is greatest in iodine
metals with valency states 3 are usually covalent halides. and least in chlorine. The covalent halides have lower melting
and boiling points than related ionic halides with isoelectronic
central elements.
4.1 Ionic Halides
Usually, covalent halides hydrolyze in aqueous solutions
In general, the greater the difference in electronegativity forming oxides or hydroxides, but many transition element
between the element and the halogen, the greater will be the halides form ionic hydrates.
charge separation and the better will be the ionic model. On
the other hand, with an increase in the formal charge on the
4.3 Covalent Polymeric Halides
central atom or with a decreasing electronegativity difference,
the better will be the covalent model. The odd coordination numbers 1, 3, and 5 are not as
The ionic halides, such as those of groups 1 and 2, exist as stable as the even coordination numbers 2, 4, and 6 (see
involatile solids with a three-dimensional lattice, whereas the Coordination Numbers & Geometries). Therefore, binary
semiionic halides, such as those of groups 11 and 12, form covalent halides of group 13 and 15 elements, MX3 and
layers and chain structures. MX5 , tend to dimerize into M2 X6 (1) and M2 X10 (2), the
In a series of the more ionic halides with the same metal, central atoms having coordination numbers of four or six,
the melting and boiling points decrease with the increasing respectively. In these dimers, halogen-bridging bonds exist in
atomic number of halogen, following the sequence MFn > addition to the terminal halogen bonding.
MCln > MBrn > MIn ; in a covalent series this sequence will
be reversed: MIn > MBrn > MCln > MFn .
Ionic halides dissolve easily in polar coordinating solvents X X X
X X
with a high dielectric constant, such as water, whereas the X X X
M M M M
covalent halides dissolve better in nonpolar, organic solvents. X X X
X X X
Halide anions can also react with covalent halides to form X X
complexed anionic species. (1) (2)
6 CHLORINE, BROMINE, IODINE, & ASTATINE: INORGANIC CHEMISTRY
Most preparations take place by direct reaction of the two Compound Mp ( C) Bp ( C) Form at room temp.
elements to form binary interhalogens (equations 27 and 28). ClF 155.6 100.1 Colorless gas
Since the reactions between the same pair of halogens are BrF 33 20 Pale brown gas
equilibria, interhalogens with different compositions can be BrCl 66 5 Red-brown gas
formed, depending on the working conditions such as relative ICl 27.2 100 Ruby red crystals
concentrations, temperature, and pressure (equations 29 32). IBr 41 116 Black crystals
ClF3 76.3 11.8 Colorless gas/liquid
BrF3 8.8 125.8 Straw-colored liquid
I2 + Br2 2IBr (27) I2 Cl6 101 Dissociates Bright yellow solid
I2 + 3Cl2 I2 Cl6 (28) ClF5 103 13.1 Colorless gas
BrF5 60.5 41.3 Colorless liquid
200 300 C IF5 9.4 104.5 Colorless liquid
X2 + 3F2 2XF3 (X = Cl, Br) (29)
IF7 6.5 4.8 Colorless gas
78 C
I2 + 3F2 2IF3 (30)
350 C
Cl2 + xs F2 2ClF5 (31) example of a halogen monofluoride structure. The structure is
250 atm not like - or -ICl or IBr. The ClF molecules form infinite
25 C planar ribbons characterized by very short intermolecular
I2 + 5F2 2IF5 (32)
Cl Cl contacts [3.070(1) A].17
5.1.1 Diatomic Interhalogens XY 5.1.2 Halogen Fluorides XF3 , XF5 , and IF7
All six possible interhalogens of this type exist. Out Four tetraatomic interhalogens are known, namely, ClF3 ,
of these, the gaseous ClF is very stable, ICl and IBr are BrF3 , IF3 , and ICl3 , which is actually the solid dimer I2 Cl6 .
moderately stable and are pure crystalline materials at room ClF3 and BrF3 are well-characterized volatile molecular
temperature, whereas BrCl dissociates easily and reversibly liquids with a T-shaped structure (3). However, the related
into its elements (equation 36); BrF and IF disproportionate ICl3 exists only as the solid dimer I2 Cl6 with a planar
into a higher fluoride and Br2 or I2 (equation 37). IBr, a structure (4) containing four terminal ICl bonds and two
solid resulting from direct combination of the elements, is bridging IClI bonds with differing bond distances. The
endothermic and extensively dissociated in the vapor. The halogen fluorides are extremely powerful fluorinating agents.
structure of ClF, determined at 188 C, represents the only In particular, ClF3 acts as such even at room temperature,
8 CHLORINE, BROMINE, IODINE, & ASTATINE: INORGANIC CHEMISTRY
while reacting elemental fluorine, under similar conditions, 5.2 Polyhalogen Cations1921
may require some preheating. This extreme reactivity of ClF3
seems to result from the fact that it is in equilibrium with Cation formation is not restricted, as normally observed,
the dissociated species, ClF, and fluorine atoms, the fluorine to association with metallic species. It can also occur among
radicals being more reactive than molecular fluorine itself nonmetals and even the most typical ones such as halogens
(equation 44). or interhalogens, which are usually more noted for halide and
polyhalide anion formation.
ClF3 ClF + 2F (44)
There are two kinds of polyhalogen cations. The
isopolyhalogen cations contain several atoms of the same
halogen, whereas the heteropolyhalogen cations contain
F several atoms of at least two different halogens.
Cl Cl Cl The formation of these cations can be considered as being
X F I I derived from the self-ionic dissociation of the neutral halogens
F Cl Cl Cl or interhalogens (equation 45). As with the interhalogens, the
(3) (4)
central atom is always the heavier and less electronegative
one, even if this causes an unsymmetrical structure such as
ClClF (instead of ClFCl; equation 46). Sometimes the
As shown in Figure 4, IF3 has a polymeric structure derived cation becomes polymerized, as in [I3 Cl2 ]+ , which
based on planar T-shaped molecules [FIF = 160.3(2) ]. is a derivative of ICl (equation 47). In the case of elemental
Intermolecular interactions to two adjacent molecules occur, halogens, several ionic equilibria are possible, and different
which result in an unusual planar pentagonal coordination isopolyhalogen cations can be obtained from the same halogen
geometry around the iodine atom; this is quite unlike that seen (equations 48 50) depending on reaction conditions such as
for BrF3 or ClF3 .18 the acidity of the reactants. All the different varieties of such
All the halogens form hexaatomic halogen fluorides ClF5 , cations have been synthesized, characterized, and studied.
BrF5 , and IF5 , with a square pyramidal structure of C4v
symmetry, but IF7 is the only one known with the highest 2XYn [XYn1 ]+ + [XYn+1 ] (45)
+
coordination number of seven. This latter compound has a 3ClF [Cl-Cl-F] + [F-Cl-F] (46)
pentagonal bipyramidal structure with D5h symmetry. All +
4ICl [I3 Cl2 ] + [ICl2 ] (47)
the halogen fluorides are very vigorous fluorinating agents, 3X2 [X3 ]+ + [X3 ] (48)
the least of them being IF5 . The order of reactivity is +
4X2 [X5 ] + [X3 ] (49)
approximately ClF3 > ClF5 > BrF5 > IF7 > ClF > BrF3 >
+
IF5 > BrF > IF3 > IF. 5X2 2[X2 ] + 2[X3 ] (50)
from elemental halogens or from diatomic interhalogens. Br2 + IOSO2 F [IBr2 ]+ [SO3 F] (68)
An oxidizer is required in addition to the Lewis acid BrF5 + 2SbF5 [BrF4 ]+ [Sb2 F11 ] (69)
(equations 54 58), but sometimes the Lewis acid itself can +
ClF5 + PtF6 [ClF6 ] [PtF6 ] (70)
also serve as an oxidizing agent (equations 59 and 60). Some
heteropolyhalogen cations can also be obtained by oxidation 2ClF5 + 2PtF6 [ClF6 ] [PtF6 ] + [ClF4 ] [PtF6 ]
+ +
(71)
reactions (equation 61).
BrF5 + [KrF]+ [AsF6 ] [BrF6 ]+ [AsF6 ] + Kr (72)
+ +
7I2 + KIO3 + 8AlCl3 5[I3 ] [AlCl4 ] (54) IF7 + BrF3 [IF6 ] [BF4 ] (73)
in HSO3 F SbF5
X2 + S2 O6 F2 [X3 ]+ [Sb3 F16 ] (55) Heteropolyhalogen cations with coordination numbers 4
78 C exist only with fluorine ligands, namely, [XF4 ]+ and [XF6 ]+
Cl2 + ClF + AsF5 [Cl3 ]+ [AsF6 ] (56)
(X = Cl, Br, and I). The pentaatomic polyhalogen cations
+ +
3
2
Br2 + [O2 ] [AsF6 ] [Br3 ] [AsF6 ] + O2 (57) [XF4 ]+ have a pseudo-trigonal bipyramidal structure (6) with
Au(s) + 4BrSO3 F [Br3 ]+ [Au(SO3 F)4 ] + 12 Br2 (58) C2v symmetry, two fluorines being in the axial positions and
two others in the equatorial triangular plane.
3I2 + 3MF5 2[I3 ]+ [MF6 ] + MF3 (M = As, Sb)
(59)
2I2 + xs SbF5 2[I3 ]+ [Sb2 F11 ] (60) Y +
+
X F4 F12
Y Y
C1
(5) F5
F3
Sb
It is interesting to note that oxidation reactions (equa- F11
tions 62 73) can produce heteropolyhalogen cations such as F2
[IBr2 ]+ , [ClF6 ]+ , and [BrF6 ]+ , although their parent inter-
F13*
halogens, IBr3 , ClF7 , and BrF7 , have never been isolated.
F1
+ +
[Br3 ] [Au(SO3 F)4 ] + Br2 [Br5 ] [Au(SO3 F)4 ] (62)
8Br2 + 3[XeF]+ [AsF6 ] 3[Br5 ]+ [AsF6 ] + 3Xe + BrF3 (63)
F4*
2I2 + ICl + AlCl3 [I5 ]+ [AlCl4 ] (64)
2ClF + AsF5 [FCl2 ]+ [AsF6 ] (65)
+ Figure 5 A view of the solid-state structure of [ClF4 ]+ [SbF6 ] .
I2 Cl6 + 2SbCl5 2[ICl2 ] [SbCl6 ] (66)
(Reprinted with permission from Ref. 22. 2001 American
ClF3 + AsF5 [ClF2 ]+ [AsF6 ] (67) Chemcial Society)
10 CHLORINE, BROMINE, IODINE, & ASTATINE: INORGANIC CHEMISTRY
The isopolyhalide anions can be prepared by reacting A solid polyhalide salt with the structure M+ [Xm Yn Zp ]
elemental halogen with the same monoatomic halide tends to dissociate into a simple monohalide derivative of
(equation 74). As mentioned before, polyhalide anions are the the cation M+ with the most electronegative halogen, and a
counterions of the self-dissociation process of interhalogens, neutral halogen or interhalogen.
and as such their preparation can take place by reacting The stability of various polyhalide compounds with the
an interhalogen with a Lewis base (equations 75 77). Some same cation are as follows: [I3 ] > [IBr2 ] > [ICl2 ] >
heteropolyhalides can be prepared by oxidation of simple [I2 Br] > [Br3 ] > [BrCl2 ] > [Br2 Cl] . The most stable
halide anions (equations 78 and 79). The unique [IF8 ] anion compounds are those with iodine at the center. Similarly, the
can be made as its Me4 N+ salt by interaction of IF7 with symmetric anions are more stable than the asymmetric ones,
Me4 NF in MeCN. [ClBrCl] > [BrBrCl] .
It is well known that a wide range of polyhalides
X2 + X [X3 ] (74) exist for iodine, and most of these can be considered
+ +
as arising from combinations of I2 , I , and [I3 ] .
[Et4 N] Cl + ICl3 [Et4 N] [ICl4 ] (75)
Linear [I3 ] anions have been identified in numerous
+
KF + BrF3 K [BrF4 ] (76) compounds such as Co(C6 H12 S3 )(I3 )2 ,28 [Prn Me2 PhN](I3 ),29
MCl + 2F2 +
M [ClF4 ] (M = K, Rb, Cs) (77) and Ag([18]aneS6 )(I3 ).30 The [I4 ]2 anions are present in
6MCl + xs 8BrF3 6M+ [BrF4 ] + 3Cl2 + Br2 (M = K, Ag, 12 Ba)
[Cr(NH3 )6 ](I3 )(I4 )31 and [NH4 ]2 [(AuI4 )AuI2 (-I4 )].32
(78)
The V-shaped pentaiodide anions in [{Rh(-pz)I(CO)-
(PMe2 Ph)}2 ][I5 ],33 [(Bu3 PSe)2 I][I5 ],34 [C19 H16 FeNS][I5 ],35
IF7 + Me4 NF [Me4 N]+ [IF8 ] (79)
and [EtMe3 N][I5 ]36 form extended polymeric layers, while
[EtMePh2 N][I5 ] is of the rare isolated types.37
In all the heteropolyhalide anions, the central atom The anionic networks identified for (DMFc)4 (I26 )38
is always the heavier and least electronegative halogen. and Ag([18aneS6 ])(I7 ),30 despite the significantly different
Although three reactions (equations 80 82) with different empirical compositions, are quite similar. For the former
starting anions can occur, a single anionic product, [ICl2 ] , (Figure 6), the network may be derived from a primitive
is obtained and no isomers are identified. The structure of cubic lattice of iodide ions with I2 bridges on all edges by
[PPh4 ][ICl2 ] shows an anion that is symmetric and nearly systematically removing 1/12 of the I2 molecules, while for
linear [ClICl = 178.10(6) ].27 the latter the iodide ions occupy the lattice points of a primitive
rhombohedral lattice with I2 bridges along all edges.
KI + Cl2 K+ [ICl2 ] (80) Cations embedded in a three-dimensional polyiodide
PBr5 + IBr [PBr4 ]+ [IBr2 ] (81)
network of cages of [I5 ] ions and diiodine molecules are
+ +
presented in [RhCl2 (C12 H24 S4 )](I5 )I2 .39 In [Pri Me2 PhN](I8 ),
K [ICl4 ] + KI 2K [ICl2 ] (82)
the anion is best described as [I16 ]2 , which is present as 14-
membered rings, catenated by diiodine molecules, and linked
Astatine interhalogens AtY (Y = Br and I) also react into layers with 10-membered and types of 14-membered
with I , Br , and Cl to form heteropolyhalide anions rings.30 In [Pd2 Cl2 ([18aneN2 S4 ])1.5 I5 (I3 )2 , infinite chains of
CHLORINE, BROMINE, IODINE, & ASTATINE: INORGANIC CHEMISTRY 11
*
*
* *
*
The [I22 ]4 anion in [MePh3 P]4 I22 consists of two L-shaped Similar reactions lead to the formation of HBr and HI.
[I5 ] units bridged by an iodine molecule and completed by The latter can also be prepared by reacting the element with
two end-on [I5 ] groups.47 phosphorus and water (equation 88, X = Br or I).
Much larger iodine catenates are obtained when metal
iodides are present; the reaction of TlI with (Me3 S)I7 2P + 6H2 O + 3X2 6HX + 2H3 PO3 (88)
resulted in a number of species from which (Me3 S)3 I26
has been structurally characterized, and shown to be of Isotopic variants of the hydrohalides, such as with
[I5 ] and [I7 ] anions with intercalated iodine molecules.48 deuterium and tritium, can be prepared by hydrolytic reactions
A mixture is identified in [Me3 PNHPMe3 ]4 (I28 ), the linear of covalent halides such as PX3 , PX5 , AlCl3 , and PhCOCl
[I3 ] , the Z-shaped [I8 ]2 , and the zigzag chains of with D2 O or T2 O (equation 89).
[I14 ]4 .49 In [Cp2 Fe]3 [I29 ], the most iodine-rich polyiodide,
PhCOX + D2 O DX + PhCO2 D (89)
the ferrocenium cations, are made to interact in the cavities of
an anionic three-dimensional network cage structure described
by the formula [{(I5 )1/2 I2 }{(I12 2 )1/2 I2 }I2 ].50
Discrete linear symmetric [ICl2 ] anions have been 6.1 Physical Properties of Hydrogen Halides
reported in [H2 Phen][ICl2 ]Cl51 and [Hphen]2 [ICl2 ][I2 Cl].52
Whereas the heavier HX are diatomic gases at room
For later, the columnar stacking of cations produces cavities
temperature, HF is a volatile liquid boiling at 19.5 C. This
for the [ICl2 ] anions and channels in which the polyanionic
exceptional property of HF is explained on the basis of its
[I2 Cl] chains are found. Unremarkable anionic geometries
polymeric structure (HF)x , due to the very strong FHF
are reported in [Pd(C6 H12 S3 )2 ](IBr2 ), [Pd(C10 H20 S4 )](IBr2 ),53
hydrogen bonding (see Fluorine: Inorganic Chemistry). The
and [Cs(18-crown-6)](ICl2 ).54
order of the boiling and melting points of the hydrogen halides
The structure of [PPh4 ][I3 Br4 ], derived from the reaction
is HF > HCl < HBr < HI. This trend also exists for the group
of [PPh4 ]Br with IBr, has a seven-membered polybromide
16 and 15 hydrides, namely, H2 O > H2 S < H2 Se < H2 Te
[I3 Br4 ] with a distorted C3v symmetry, which is best
and NH3 > PH3 < AsH3 < SbH3 . This is in contrast to the
described as a bromide coordinated to three IBr units via
properties of the hydrides of group 14, in which the order
the iodine atoms.55
is as expected, that is, CH4 < SiH4 < GeH4 < SnH4 . The
discontinuity results from the fact that hydrogen bonds can be
formed easily with the lighter elements, F, O, and N. Some
physical properties of the hydrogen halides are summarized
6 HYDROGEN HALIDES in Table 5. All are colorless, fume easily with moist air, and
have penetrating odors.
The name hydrogen halides, HX, is used for the anhydrous
compounds, whereas their aqueous solutions are called
hydrohalic acids. In their anhydrous condition, these are 6.2 Nonaqueous Solvents56
molecular compounds, whereas solutions in water bring about
ionic dissociation to give the protonated solvent and the halide Except for hydrogen fluoride, the hydrogen halides have
anion (equation 84). only a limited use as nonaqueous solvents. AHF plays an
important role as a nonaqueous solvent57 in fluorine chemistry,
HX + H2 O [H3 O]+ + X (84)
and it also serves as an important liquid medium for numerous
synthetic preparations. It is easily handled owing to its boiling
point (19.5 C) being close to ambient temperature, and is a
Hydrogen chloride is produced industrially on a huge scale liquid under its own vapor pressure; it has a long liquid range of
and is used as the anhydrous gas as well as a hydrochloric acid about 100 C, has low viscosity, and a high dielectric constant.
in aqueous solution. Several industrial routes to synthesize The physical properties of AHF therefore make it an excellent
HCl are in use: (1) direct burning of hydrogen in chlorine, solvent for both inorganic polar solutes as well as organic
which results in a very pure product (equation 85); (2) reaction nonpolar solutes, compounds, and even biological materials.
of an inorganic metal halide with a less volatile protic acid,
such as sulfuric acid, to form the more volatile hydrogen halide
Table 5 Physical properties of the hydrogen halides
(equation 86) and (3) as a by-product of the chlorination of
hydrocarbons (equation 87). Property HF HCl HBr HI
The properties of all other hydrogen halides are far removed acid in the stomach, for example, is extremely important
from those of AHF and, therefore, their use as nonaqueous in the digestive system, and iodine is of importance in
solvents is rather limited. Nevertheless, they are used for thyroid function.
physical studies of solutions and for some synthetic purposes,
such as in the formation of salts with HCl2 or BCl4 and
related anions. Anhydrous HX can be considered to undergo
self-ionization (equation 90) and can therefore be used to 7 HALOGEN OXIDES
perform reactions of an acid base nature, and solvolytic and
redox reactions (equations 91 93).
A large number of binary halogen oxides are known, from
3HX +
[H2 X] + [HX2 ]
(90)
shock-sensitive liquids to rather stable solids. Similarly, a
large number of oxoacids and oxoacid salts are also known.
SbF3 + 3HCl SbCl3 + 3HF (91)
Most halogen oxides are not very stable and decompose
I + 2Cl2 [ICl4 ] (92) easily. This stems from the fact that the number of electrons
+ in these molecules is an odd number. Therefore, the ions
PCl3 + X2 + HCl [PCl3 X] + [HClX] (X = Cl, Br) (93)
formed by the addition of an electron, whether in oxoacids or
in oxoacid salts, are more stable.
6.3 Hydrohalic Acids Dichlorine oxide, Cl2 O, is best prepared on a laboratory
scale by reacting chlorine with mercury oxide (equation 94).
Hydrohalides dissolve easily in water to form hydrohalic
On an industrial scale, it can be prepared by reacting chlorine
acids and undergo virtually complete ionic dissociation
with moist carbonate (equation 95). This oxide is readily
(equation 84). All the hydrohalic acids, except HF, are very
soluble in water to form hypochlorous acid (equation 96).
strong acids. Although AHF is one of the most acidic liquids,
Its salts, the hypochlorites, are quite stable and are used in
as measured by its Hammett function, hydrofluoric acid is a
the textile industries and to bleach wood pulp. The low-
weak acid.
temperature crystal structure of Cl2 O reveals an essentially
Hydrochloric acid is of great importance and is widely used
molecular structure [d(OCl) = 1.7092(4) A] with weak
in industrial processes. The largest use is in the metallurgical
secondary interactions [d(O Cl) = 2.7986(4) A] affording
industry for the pickling of metals to remove oxide scales.
a distorted tetrahedral coordination around the O atom.58
Other uses include the production of inorganic halides from
metals, oxides or carbonates, extraction of metals from ores
2Cl2 + 2HgO HgCl2 HgO + Cl2 O (94)
in metallurgical processes, and various organic reactions.
Hydrobromic acid is used in the production of inorganic 2Cl2 + 2Na2 CO3 + H2 O 2NaHCO3 + 2NaCl + Cl2 O (95)
bromides as well as in organic brominations, particularly in Cl2 O + H2 O 2HOCl (96)
the production of pesticides. Some physical properties of the
hydrohalide acids are summarized in Table 6. Cl2 O3 , generated in the reaction of ClO with ClO2 , has a
relatively short lifetime and is not expected to be an important
6.4 Biological Action reservoir for ClOx .59
Chlorine dioxide, ClO2 , is a stable oxide and can be
In addition to their action on the respiratory system and prepared by reducing chlorates (equation 97) or in reaction
attacking the mucous membrane and skin, a major hazard of with moist oxalic acid (equation 98). Chlorine dioxide is a
concentrated hydrohalic acids is direct contact with the skin, strong oxidizing agent toward both organic and inorganic
causing chemical burns. Some of these compounds, however, materials.
are important in biochemical processes. The hydrochloric
[ClO3 ] + Cl + 2H+ ClO2 + 12 Cl2 + H2 O (97)
Table 6 Physical properties of hydrogen halides in aqueous solution [ClO3 ] + [C2 O4 ]2 ClO2 (98)
by low-temperature distillation at low pressure. Dissolution (IO)2 SO4 has been shown to hydrolyze to a pow-
in water or alkali again produces the acid or perchlorates der formulated as I2 O4 , which is monoclinic and
respectively. Table 7 summarizes some physical properties thought to have a one-dimensional structure compris-
of the chlorine oxides. The ClO4 radical is generated by ing alternating oxygen-bridged iodine(I) and iodine(V) units
thermal decomposition of Cl2 O6 or Cl2 O7 in Ar or Ne. It has a IOIO2 O(IOIO2 O)n IOIO2 O. It decomposes on
lifetime of only a few milliseconds but could be obtained in a heating to I2 O5 and I2 (equations 101 and 102).65
matrix at low temperature and characterized by IR and UV/VIS
specptroscopies, and indicates a dynamic Jahn Teller effect.60 4(IO)2 SO4 + 4H2 O 4H2 SO4 + I2 + 3I2 O4 (101)
Bromine forms oxides such as Br2 O, Br2 O3 , and BrO2 , and 5I2 O4 I2 + 4I2 O5 (102)
these are less well characterized than for chlorine. They are
stable at low temperatures but unstable at room temperature.
Reaction of H5 IO6 with H2 SO4 results in IO3 , whose
For example, compound Br2 O3 (synthesized from Br2 and O3 )
structure consists of I4 O12 units (two IO6 octahedra sharing
has been shown to form as an orange crystalline solid and on
an edge and two pyramidal IO3 groups sharing two vertices
further ozonization to give a colorless oxide, which does not
with the double octahedron) linked through I O bridges, and
contain the colored OBr(I) unit. It is insoluble in CH2 Cl2 ,
may be considered to be the mixed anhydride of H5 IO6 and
unlike Br2 O3 , and decomposes above 40 C. However, it can
HIO3 .66
be crystallized from propionitrile as Br2 O5 (EtCN)3 and the
structure determination shows symmetric O2 BrOBrO2 to be
present. The molecule has terminal bonds (1.62 A), which are 7.1 Halogen Oxide Cations
shorter than the bridging ones (1.87 1.89 A). The bond angle
at the bridging oxygen atom is 121 . This study brings into Reacting halogen oxides with Lewis acids or dissolving
doubt the existence of Br2 O4 , which has a Raman spectrum them in superacids such as fluorosulfonic acid or persulfuric
very similar to that of Br2 O3 .61 The gas-phase FTIR spectra of acid produces the halogen oxide cation [ClO2 ]+ , as in
two important bromine-containing species, OBrO and Br2 O, [ClO2 ]+ [SO3 F] , [ClO2 ]+ [SbF6 ] , and [ClO2 ]+ [BF4 ] .
have been reported.62 The hydrolysis of BrOTeF5 offers a new Other cations have also been identified, such as [ClO]+ .
route to Br2 O. X-ray analysis shows that the compound is bent The reaction of Cl2 with [O2 ]+ [SbF6 ] forms [Cl2 O2 ]+
[114.2(2) ] with strong Br Br interactions in the solid state [SbF6 ] or [Cl2 O2 ]+ [Sb2 F11 ] (Figure 9).67 In the reaction
resulting in chains.63 of iodine oxide with SO3 or S2 O6 F2 , the cation [IO2 ]+ is
For the bromine oxides, the realization that the only well- formed, but when dissolved in concentrated sulfuric acid the
characterized compounds use all the possible combinations reduced [IO]+ cation is formed. Whereas the chlorine oxide
of the only basic units in this area (i.e. terminal OBr cations are discrete ions, the iodine oxide species appear to be
and pyramidal OBrO2 in BrOBr, BrOBrO2 and polymerized, with IOI bridging networks, cross-linked to
O2 BrOBrO2 ) suggests that new homoleptic bromine oxides the anions.
are likely to be even less stable than these derivatives.64
Iodine forms the most stable of all halogen oxides, I2 O5 ,
7.2 Halogen Oxide Fluorides
which exists as white, hygroscopic crystals. It can be prepared
by dehydration of iodic acid, HIO3 , at 200 C in a stream Halogen oxides can be reacted with fluorine or halogen
of air. It can also be prepared by direct interaction of iodine fluoride to form halogen fluoride oxides, Fn XOm . Similar to
and oxygen in a glow discharge. I2 O5 dissolves easily in the halogen fluorides, the central atom is always that of the
water to form the parent compound (iodic acid). It can
oxidize various inorganic chemicals and is one of the few
agents that oxidizes carbon monoxide completely at room 2.425(11)
CI2 (2.414(4))
temperature (equation 100). This reaction is used to analyze
O2
the concentration of CO in air or in gaseous mixtures.
1.916(5) 1,185(11)
5CO + I2 O5 5CO2 + I2 (100) (1.909(1)) 1.207(5))
heavier halogen bonded directly to fluorine and to oxygen. stable is BrClO3 , which can be prepared by fluorination of
Halogen oxide fluorides can be considered to undergo self- perbromate with AsF5 or BrF5 (equation 109).
ionization, similar to interhalogens (equation 103), and can
thus react with Lewis acids and bases to form the appropriate KBrO4 + 2AsF5 + 3HF FBrO3 + [H3 O]+ [AsF6 ] + KAsF6
salts. (109)
O(1c)
7.3.2 Halous Acids and Halites
Figure 10 View of the solid-state structure of IO2 F, showing the This group of compounds is the least stable of the various
interactions between adjacent molecules. (Reprinted with permission oxoacids and oxoacid salts, and is restricted to chlorous acid
from Ref. 69. 2001 American Chemcial Society) and its salts. Barium chlorite is prepared by reacting ClO2 with
a basic solution in the presence of H2 O2 , which serves as a
reducing agent (equation 115). Adding dilute sulfuric acid to a
7.3 Oxoacids and Oxoacid Salts68 suspension of Ba(ClO2 )2 forms chlorous acid (equation 116).
The oxoacids and their salts are very stable, in contrast to Ba(OH)2 + H2 O2 + 2ClO2 Ba(ClO2 )2 + H2 O + O2 (115)
the lack of stability of the halogen oxides themselves. A large
Ba(ClO2 )2 + H2 SO4 2HClO2 + BaSO4 (116)
number of these acids exist at the representative oxidation
states of the halogens, namely, +1, +3, +5, and +7. Even
perbromic acid, HBrO4 , has been synthesized by fluorination Anhydrous NaClO2 crystallizes out of solution above
of bromates. room temperature and serves as an oxidizing agent toward
malodorous and toxic organic compounds.
Although bromous acid itself is unknown, Ba(BrO2 )2 and
7.3.1 Hypohalous Acids and Hypohalites the corresponding strontium salt can be prepared by treating
hypobromite with Br2 in strongly basic solutions at 0 C,
The easiest preparation of aqueous solutions of the followed by slow evaporation.
hypohalous acids is to dissolve the appropriate halogen in
water (equation 112).
7.3.3 Halic Acids and Halates
+
X2 + H2 O HOX + H + X (112)
Introducing a halogen into a hot basic solution causes a
disproportionation process. Part of the halogen is reduced to
The addition of silver or mercury oxide precipitates the the halide anion and another part of it is oxidized to the halate
metal halide, leaving behind the aqueous solution, which anion (equation 117).
is very reactive and is used for bleaching and sterilizing
purposes. Solutions of hypohalites can be made by introducing 3X2 + 6OH [XO3 ] + 5X + 3H2 O (117)
the appropriate halogen into basic solutions (equation 113),
but these will also contain some halide anions. To obtain Chlorate is the most important halate and is produced,
pure hypochlorites, it is necessary to carefully neutralize pure on an industrial scale, by electrolysis of a halide solution
hypochlorous acid. The most stable hypochlorites are those of in a diaphragmless cell, which promotes efficient mixing.
Li, Ca, Sr, and Ba, although some others are also known but This arrangement allows the chlorine produced at the anode
are not as stable, or are not sufficiently pure. to react with the hydroxyl anion at the cathode, forming
the hypochlorous anion, which is then further oxidized to
X2 + 2OH OX + X + H2 O (113) chlorate, whether by oxidation at the anode or through
CHLORINE, BROMINE, IODINE, & ASTATINE: INORGANIC CHEMISTRY 17
08*
Salts such as KBrO4 (dec. 275 C) and NH4 BrO4 (dec. 08*
170 C) are fairly stable thermally and isomorphorus with 07*
07*
their perchlorate analogues. However, potassium perbromate
is thermodynamically less stable than both the corresponding 05*
05*
perchlorate and periodate analogues. 07*
07*
08* 08*
At least four series of periodates interconnected in aqueous 06*
solution by a complex series of equilibriums are known.
All these are derived from the parent acid H5 IO6 through
deprotonation, dehydration, and aggregation; some are listed
in Table 9. Figure 11 An ORTEP drawing of a single disordered [IO4 ] anion
showing a detailed view of the rotational disorder about one IO
The industrial preparation is based on electrolytic oxidation axis. (Reprinted with permission from Ref. 73. 2001 American
(equation 122) or with chlorine (equation 123). Chemcial Society)
8 ORGANIC POLYVALENT HALOGEN Dissolving an ArICl2 in basic solution forms the iodoso
DERIVATIVES compound, ArIO (equation 128). Another synthetic procedure
to obtain iodoso compounds is by direct oxidation of ArI with
The intention is not to cover the vast halo-organic ozone, fuming nitric acid, or KMnO4 .
chemistry in this context, but only organic polyvalent halogen
compounds that are actually limited to derivatives with iodine ArICl2 + OH ArIO (128)
(I), iodine (III), and iodine (V), though evidence for the
divalent L2 I radical was obtained by the hemolytic cleavage of ArI(OAc)2 can be crystallized from a solution of either
IO bonds during thermolysis of tert-butyl-peroxyiodanes.76 ArICl2 or ArIO in acetic acid. ArI(ONO2 )2 can be obtained
by reacting silver nitrate with a solution of those iodine
compounds in acetonitrile.
8.1 Monovalent Iodine
Although Br+ has been postulated to occur in reactions 8.2.2 Diorganohalonium Compounds
of Br2 , the evidence is usually only kinetic. However, the
solvated linear ions [L2 Br]+ and [L2 I]+ , where L may be Diaryliodonium compounds can be prepared by acid-
pyridine, MeCN, quinuclidine, and so on are known.77 The catalyzed condensation of iodoso aryls with another aryl
oxidants [I(MeCN)2 ]+ [UF6 ] can be prepared from reactions molecule (equation 129). Another method is the use of
of UF6 with 1/2 equiv of I2 in MeCN. But Br+ is too iodine trichloride in reaction with organometallic compounds
electrophilic to exist in MeCN. The reaction in liquid SO2 (equations 130 and 131). RICl2 may be prepared by direct
gives a 95% yield of the salt [I(MeCN)]+ [AsF6 ] .78 chlorination of RI (R = CF3 CH2 , CHF2 (CF2 )5 CH2 ) and these
materials can be used to chlorinate iodobenzene to give the
less hydrolytically stable compound PhICl2 .80
8.2 Trivalent Iodine
HX
Trivalent iodine compounds can be divided into the ArIO + Ar H ArAr IX + H2 O (129)
following categories: (1) with one carbon iodine bond, such
Ar2 Hg + ICl3 Ar2 ICl (130)
as in iodo salts, RIX2 , and iodoso compounds, RIO; (2) with
two carbon iodine bonds on the same iodine, such as RR IX; CF3 CH2 I + Cl2 CF3 CH2 ICl2 (131)
and (3) with three carbon iodine bonds on the same iodine,
such as Ph3 I. Diaryliodonium compounds are good arylating agents,
introducing a second aryl group where one already exists
(equation 132).
8.2.1 Iodo Disalts
Ph2 ICl + PhOH Ph2 O + PhI + HCl (132)
Aromatic iodo disalts, ArIX2 , can be prepared by passing
chlorine into an organic solution of an aryl iodide, ArI
(equation 124). On standing, the material decomposes into Among the compounds in which I3+ is combined with
HCl and a chlorine-substituted aromatic part (equation 125). oxoanions are I(OSO2 F)3 , I(NO3 )3 , I(OCOCH3 )3 , IPO4 , and
I(OClO3 )3 (equations 133 137). These compounds contain
ArI + Cl2 ArICl2 (124) essentially covalent IO bonds. Preparative routes are shown
C6 H5 ICl2 p-ClC6 H4 I + HCl (125) as followings. These compounds are very sensitive to moisture
and are not stable much above room temperature. They are
Iodobenzene dichloride can be used as a mild chlorinating hydrolyzed with disproportion of the I3+ , as shown for IPO4
agent in organic synthesis. From vibrational spectroscopy,79 (equation 138).
it seems that the ArICl2 has a T-shaped structure in which
2I2 + 3AgClO4 I(OClO3 )3 + 3AgI (133)
the ClICl is linear and the phenyl group is perpendicular
to it. Such a structure could be attributed to a partially ionic I2 + 6ClOClO3 2I(OClO3 )3 + 3Cl2 (134)
compound with the halide part being an anion, [ClICl] , CsI + 4ClOClO3 Cs[I(OClO3 )4 ] + 2Cl2 (135)
and the phenyl unit more positively charged. This physical I2 + HNO3 (fuming) + (CH3 CO)2 O I(OCOCH3 )3 (136)
structure has also been established by X-ray data.
I2 + HNO3 (conc) IPO4 (137)
Perfluoroalkyl iododifluorides can be prepared with
halogen fluorides (equation 126). Using an excess of halogen 5IPO4 + 9H2 O I2 + HNO3 + 5H3 PO4 (138)
fluoride, the iodotetrafluoride is obtained (equation 127).
The structure of I(OCOMe)3 is T-shaped as expected with
Rf I + XFn Rf IF2 (126) three primary IOC bonds and longer IO interactions. In
Rf I + xs XFn Rf IF4 (127) [Bu4 N][I(OTeF5 )4 ], the anion has a square IO4 unit.
20 CHLORINE, BROMINE, IODINE, & ASTATINE: INORGANIC CHEMISTRY
33. C. Tejel, M. Bordonaba, M. A. Ciriano, A. J. Edwards, 57. H. H. Hyman and J. J. Katz, in Non-aqueous Solvent Systems,
W. Clegg, and F. J. Lahoz, Inorg. Chem., 1999, 38, 1108. ed. T. C. Waddington, Academic Press, London, 1965, Chap. 2,
34. E. Seppela, F. Ruthe, J. Feske, W. W. DuMont, and P. G. Jones, p. 47.
Chem. Commun., 1999, 1471. 58. R. Minkwitz, R. Bochler, and H. Borrmann, Z. Kristallogr.,
35. R. Richter, O. Seidelmann, and L. Beyer, Z. Anorg. Allg. Chem., 1998, 213, 237.
1999, 625, 511. 59. M. H. Harwood, D. M. Rowley, R. A. Freshwater, R. A. Cox,
36. R. Loukili and K. F. Tebbe, Z. Anorg. Allg. Chem., 1999, 625, and R. L. Jones, J. Chem. Soc., Faraday Trans., 1995, 91, 4189.
650. 60. H. Grothe and H. Willner, Angew. Chem., Int. Ed., 1996, 35,
37. K. F. Tebbe and R. Louklli, Z. Anorg. Allg. Chem., 1999, 625, 768.
820. 61. D. Leopold and K. Seppelt, Angew. Chem. Int. Ed., 1994, 33,
38. K. F. Tebbe and R. Louklli, Z. Anorg. Allg. Chem., 1998, 624, 975.
671. 62. L. T. Chu and Z. Li, Chem. Phys. Lett., 2000, 330, 68.
39. A. J. Blake, W. S. Li, V. Lippolis, and M. Schroder, Acta 63. I. C. Hwang, R. Kuschel, and K. Seppelt, Z. Anorg. Allg. Chem.,
Crystallogr., Sect. C, 1998, 54, 1410. 1997, 623, 379.
40. A. J. Blake, R. O. Gould, W. S. Li, V. Lippolis, S. Parsons, 64. K. Seppelt, Acc. Chem. Res., 1997, 30, 111.
C. Radek, and M. Schroder, Angew. Chem. Int. Ed., 1998, 65. H. Fjellvag and A. Kjekshus, Acta Chem. Scand., 1994, 48,
37, 293. 815.
41. A. Grafe-Kavoosian, S. Nafepour, K. Nagel, and K. F. Tebbe, 66. T. Kraft and M. Jansen, J. Am. Chem. Soc., 1995, 117, 6795.
Z. Naturforsch., Teil B, 1998, 53, 641. 67. T. Drews, W. Koch, and K. Seppelt, J. Am Chem. Soc., 1999,
42. C. Wieczorrek, Acta crystallogr., Sect. C, 2000, 56, 1082. 121, 4379.
43. A. J. Blake, V. Lippolis, S. Parsons, and M. Schroder, Chem. 68. F. Solymosi, Structure and Stability of Salts of the Halogen
Commun., 1996, 2207. Oxyacids in the Solid Phase, Wiley, New York, 1978.
44. K. F. Tebbe and M. Essawi, Z. Anorg. Allg. Chem., 1998, 624, 69. R. Minkwitz, M. Berkei, and R. Ludwig, Inorg. Chem., 2001,
1046. 40, 6493.
45. S. Menon and M. V. Rajasekharan, Inorg. Chem., 1997, 36, 70. A. Ellern, J. A. Boatz, K. O. Christe, T. Drews, and K. Seppelt,
4983. Z. Anorg. Allg. Chem., 2002, 628, 1991.
46. K. F. Tebbe and T. Gilles, Z. Anorg. Allg. Chem., 1996, 622, 71. R. Minkwitz and M. Berkei, Eur. J. Inorg. Chem., 2001, 457.
138. 72. T. Kraft and M. Jansen, Angew. Chem. Int. Ed., 1997, 36, 1753.
47. K. F. Tebbe and T. Farida, Z. Naturforsch., Teil B, 1995, 50, 73. R. I. Wagner, R. Bau, R. Z. Gnann, P. F. Hjones, and
1440. K. O. Christe, Inorg. Chem., 1997, 36, 2564.
48. P. H. Svensson, G. Raud, and L. Kloo, Eur. J. Inorg. Chem., 74. R. Nagel, M. Botova, G. Pracht, E. Suchanek, M. M. Maneva,
2000, 1275. and H. D. Lutz, Z. Naturforsch., Teil B, 1999, 54, 999.
49. T. Grob, F. Weller, and K. Dehnicke, Z. Naturforsch., Teil B, 75. A. L. Hector, W. Levason, and M. Webster, J. Chem. Soc.,
1998, 53, 552. Dalton Trans., 1998, 3463.
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Crystallogr., Sect. C, 1999, 55, 1503. R. D. Peacock, G. Peattie, R. M. Siddique, J. M. Winfield, J.
52. C. T. McElroy, C. A. McLinden, and J. C. Schmeck, Angew. Chem. Soc., Dalton Trans., 1995, 3837.
Chem. Int. Ed., 1999, 38, 2594. 78. P. K. Gowik and T. M. Klapotke, J. Chem. Soc., Chem.
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54. M. El Essawii, K. F. Tebbe, Z. Naturforsch., Teil B, 1998, 53, Acta, 1977, 33A, 183.
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40, 25. 81. V. V. Zhdankin, A. Y. Koposov, and N. V. Yashin, Tetrahe-
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1965, Chap. 3, p. 83. Int. Ed., 2002, 43, 5735.
Chromium: Biological mobilization in the body.8 Fortunately, Cr deficiency is
difficult to develop. Recently, the Food and Nutrition Board
Relevance of the National Academy of Sciences has lowered the daily
adequate intake (AI) of Cr from 50 200 g to 25 g for
women and 35 g for men.9 These values reflect the average
John B. Vincent daily intake of Cr for Americans,3 suggesting that few
The University of Alabama, Tuscaloosa, AL, USA Americans have Cr-deficient diets. Nutritional studies have
been hampered by the lack of a biomarker for Cr status.
While Cr as the chromic ion may be essential, Cr in the
6+ oxidation state, in contrast, is a potent carcinogen and is
1 Introduction 1 present in the environment primarily as a result of human
2 Glucose Tolerance Factor 1 activity.
3 Chromodulin (Low-molecular-weight Chromium-
binding Substance) 1
4 Chromium Picolinate and Toxicity 3
5 Chromium Therapeutic Agents and Type 2
Diabetes 4 2 GLUCOSE TOLERANCE FACTOR
6 Chromate Toxicity 4
7 Related Articles 5
8 References 5 For Cr to be essential, chromic ions presumably must
bind to some biomolecule(s) and the resulting complex must
have an inherent function. The first Cr-containing species to
be proposed as this molecule was glucose tolerance factor
(GTF).10 GTF was originally extracted from porcine kidney
powder and Brewers yeast and was the subject of considerable
1 INTRODUCTION research in the 1960s and 1970s. The species was believed
to be a complex of nicotinate and amino acids and to bind
Of the transition elements proposed to be an essential trace to insulin, enhancing insulins binding to the insulin receptor.
element for mammals, Cr is probably the least understood. However, since this time, several groups have separated the
The evidence for an essential role for Cr is suggestive,1 but Cr-containing species in the yeast extracts from the insulin-
not conclusive. Four lines of evidence are usually used in stimulating factor, and GTF has been shown to be an artifact
support of an essential role. The first evidence comes from of its isolation procedure. Recently, a suggestion has been
studies in the 1990s of rats fed a purified, Cr-deficient diet made to drop the use of the term GTF.1
(33 ng Cr/g diet). In glucose tolerance tests, these rats had
elevated insulin areas compared to controls, suggesting the
onset of insulin resistance.2 Unfortunately, similar studies
before 1990, including the classic studies by Mertz that
3 CHROMODULIN (LOW-MOLECULAR-WEIGHT
originally led to the proposal that Cr was essential, have
CHROMIUM-BINDING SUBSTANCE)
methodological problems that hinder interpretation.1 Second,
Cr absorption by humans is inversely proportional to intake,
suggesting that intake is regulated.3 However, this is not The best candidate for a biologically active form of Cr is the
the case for rats.4 Next, five cases of Cr deficiency in oligopeptide chromodulin, formerly known as low-molecular-
humans have been reported.5 The subjects were all on total weight Cr-binding substance (LMWCr). Yamamoto, Wada,
parenteral nutrition (TPN), developed symptoms similar to and coworkers have demonstrated that isolated rat adipocytes
those of type 2 diabetes, and did not respond to insulin in the presence of chromodulin and insulin display an
treatment. However, the symptoms were reversed upon increased ability to metabolize glucose; this increase occurs
the addition of Cr to the TPN. The limited number of without a change in the insulin concentration required
patients, the range of blood Cr concentrations of patients, for half-maximal stimulation,11,12 suggesting a role for
and the varying symptoms have led to questions about these chromodulin inside the insulin-sensitive cells after insulin
cases.6 Finally, urinary Cr loss is directly related to blood binds externally to the insulin receptor.13 The stimulation
serum insulin concentrations.7 Increases in serum insulin of glucose metabolism by chromodulin is proportional to its
(as would result from increases in serum glucose) result chromium content.14
in increases in urinary Cr excretion. Similarly, conditions Chromodulin is a naturally occurring oligopeptide com-
that alter glucose metabolism (such as type 2 diabetes) posed of glycine, cysteine, aspartate, and glutamate with
alter urinary Cr output. Thus, a relationship appears to the carboxylates comprising more than half of the total
exist between glucose metabolism, insulin levels, and Cr amino acid residues.12,14 The lack of a published sequence
2 CHROMIUM: BIOLOGICAL RELEVANCE
is a matter of concern. Despite its small size, the molecule form. The oligopeptide is isolated as the holo-oligopeptide
has been shown to tightly bind four equivalents of chromic (so that it may be followed in the purification schemes by
ions. The binding is quite tight (K 1021 M4 ) and highly its Cr content), which means that an in vivo or in vitro
cooperative (Hill coefficient 3.47).15 Spectroscopic studies Cr-loading step is required.12,14 This observation and others
suggest that the chromic ions comprise an anion-bridged have resulted in the suggestion that chromodulin may play a
multinuclear assembly supported by carboxylates from the role in Cr detoxification; however, injection of chromic ions
oligopeptide.16 Three of the Cr centers are arranged in an or chromate into mice does not stimulate the production of
unsymmetric trinuclear assembly with the fourth mononu- apochromodulin.21 Thus, while chromodulin does carry Cr
clear center in close proximity.17 As holochromodulin can be into the urine after intake of large dosages of CrIII or CrVI
prepared simply by addition of chromic ions to solutions of and can serve to efficiently remove Cr,22 the suggested detox-
apochromodulin, these anionic bridges are probably hydrox- ification role of chromodulin is unlikely to be its primary
ide ions.13,18,19 To date, the oligopeptide has been isolated function.
and purified from mammalian liver (rabbit and bovine)12,14 Because the primary events between insulin binding to
and kidney (porcine).20 A related Cr-containing oligopep- its receptor and glucose transport are signal transduction
tide from bovine colostrum is composed of the same amino events, a role for chromodulin in these events has
acids but in distinctly different ratios and also stimulates been probed. Chromodulin activates the tyrosine kinase
insulin-dependent glucose metabolism in rat adipocytes.12 The activity of insulin-activated insulin receptor18 and activates
significance of these differences remains unexplored, and the a membrane phosphotyrosine phosphatase in adipocyte
possibility that several low-molecular-weight, carboxylate- membranes.19 The addition of bovine liver chromodulin to
rich peptides exist for the binding of Cr is in need of rat adipocytic membranes in the presence of insulin results
investigation. Chromodulin appears to be maintained in the in a concentration-dependent eightfold stimulation of insulin-
cytosol21 and nucleus22 of insulin-sensitive cells in the apo dependent protein tyrosine kinase activity (while no activation
Cr-Tf
Cr3+
I
IR IR I
Apochromodulin Apochromodulin
Lowering Apochromodulin Kf
Chromodulin of insulin concentration + 4Cr3+ ~1021 M4
in blood
Chromodulin IR I IR I
Km ~
Chromodulin
250 pM
Figure 1 Proposed mechanism for the activation of insulin receptor kinase activity by chromodulin. The inactive form of insulin receptor
(IR) is converted to the active form by binding insulin (I). This triggers a movement of Cr (in the form of Cr-transferrin, Cr-Tf ) from the blood
into cells, which in turn results in the binding of Cr to apochromodulin (triangle). Finally, holochromodulin (square) binds to insulin receptor,
further activating the receptors kinase activity. When the insulin concentration drops, holochromodulin is released from the cell to relieve its
effects. (Ref. 1. Reproduced by permission of Elsevier)
CHROMIUM: BIOLOGICAL RELEVANCE 3
of kinase activity is observed in the absence of insulin) with selectively bind to kinases and phosphatases, stimulating their
a dissociation constant of approximately 875 pM.18 Blocking activity.
the insulin-binding site on the external subunit results in
the loss of the ability to activate insulin receptor kinase
activity.16 Isolated rat insulin receptors kinase activity is
activated by bovine chromodulin in the presence of insulin 4 CHROMIUM PICOLINATE AND TOXICITY
by approximately sevenfold, conclusively demonstrating that
the receptor is the site of interaction with chromodulin. After the first studies that suggested the nutritional
Similarly, studies with a catalytically active fragment (residues supplement chromium picolinate, [Cr(pic)3 ], could have
941 1343) of the subunit of human insulin receptor reveal potentially beneficial effects on body mass and composition
that chromodulin can stimulate the kinase activity threefold. appeared in 1989,27 the nutritional supplement has become
Thus, chromodulin appears to bind at or near the kinase active amazingly popular; products containing the supplement
site.23 Cr plays a crucial role in the activation of insulin generated nearly one-half billion dollars in sales in
receptor kinase activity by chromodulin.18 Apochromodulin 1999, making the mineral supplement second only to
does not activate the receptors insulin-dependent tyrosine Ca supplements.28 Yet, studies of [Cr(pic)3 ] on healthy
kinase activity. However, titration of apochromodulin with individuals since the initial reports have failed to support
chromic ions results in the total restoration of the ability to the early findings. This has resulted in a high degree
activate kinase activity; 4 chromic ions per oligopeptide are of politicization and polarization apparent in this field. . .
required for maximal activity, consistent with the number of Cr characterized by unproven claims and counterclaims and
bound to an isolated holochromodulin. This reconstitution of suspicion among investigators. Concerns about possible
chromodulins activation potential is specific to Cr. Transition commercial interest have naturally emerged.29 Recent review
metal ions other than Cr that are commonly associated with articles1,3033 and meta-analyses3436 have concluded that the
biological systems are ineffective in potentiating the ability supplement has no demonstrated effects (body mass, body
of apochromodulin to activate kinase activity. Thus, the composition, or plasma glucose and insulin concentrations)
ability of chromodulin to potentiate the effects of insulin on healthy individuals, even when taken in combination with
is specific to Cr and is directly dependent on the Cr content of an exercise program. Yet, six years after the initial report of
chromodulin. potentially beneficial effects from [Cr(pic)3 ] supplementation,
On the basis of these results, chromodulin has been Wetterhahn and coworkers first reported potential concerns
proposed to function as part of a unique autoamplification over the use of [Cr(pic)3 ].37 The compound generated
system for insulin signaling (Figure 1).24 In this mechanism, clastogenic damage in a Chinese hamster ovary (CHO)
apochromodulin is stored in insulin-sensitive cells. In response cell model. Stohs and coworkers have demonstrated similar
to increases in blood insulin concentrations, insulin binds damage and oxidative damage in murine macrophages.38,39
Stearns, in continuing work with the CHO model, has
to its receptor, bringing about a conformation change
observed mitochondrial damage and apoptosis generated by
that results in the autophosphorylation of tyrosine residues
the supplement40 and has reported that the supplement is
on the internal side of the receptor. This transforms the
mutagenic.41
receptor into an active kinase and transmits the signal from
The effects have been postulated to arise from the
insulin into the cell. In response to insulin, Cr, stored
released picolinate ligand37,40 or from reactive oxygen
in the blood plasma bound to the iron-transport protein
species catalytically generated by the intact complex.15,42
transferrin (see Iron Proteins for Storage & Transport & Physiologically relevant concentrations of Cr as [Cr(pic)3 ]
their Synthetic Analogs), is moved from the blood into (e.g. 120 nM) and of biological reducing agents such as
cells via endocytosis.25 The Cr flux results in loading of ascorbic acid and thiols resulted in catalytic production of
apochromodulin with Cr. The holochromodulin then binds reactive oxygen species, which cleaved DNA.15,42 Most forms
to the insulin receptor, presumably assisting to maintain the of CrIII do not generate such species in the absence of a strong
receptor in its active conformation, amplifying its kinase oxidant such as peroxide.43 Hence, these studies are consistent
activity. When insulin signaling is to be turned off, a with investigations that demonstrated that mutagenic forms
drop in blood insulin levels facilitates relaxation of the of CrIII possessed chelating ligands containing pyridine-type
conformation of the receptor, and the holochromodulin is nitrogens or other imine nitrogens coordinated to the metal
excreted from the cell into the blood. Ultimately, chromodulin and generated reactive oxygen species.44 Consequently, for
is excreted in the urine. The basis of the name chromodulin this mechanism to lead to significant cell damage, [Cr(pic)3 ]
is the similarity of the proposed mechanism to that of needs to enter cells intact and remain intact long enough
the calcium-binding protein calmodulin.26 Both bind four to produce a significant quantity of reactive oxygen species.
equivalents of metal ions in response to a metal ion flux; Recently, [Cr(pic)3 ] has been shown to be able to rapidly
however, the four Ca ions that bind to the larger protein pass from the bloodstream and enter cells intact, although the
calmodulin rest in mononuclear sites. Both holoproteins lifetime of the complex in cells is short.45 In hepatocytes, Cr
4 CHROMIUM: BIOLOGICAL RELEVANCE
from [Cr(pic)3 ] first appears in the nucleus and mitochondria, from supplementation, suggesting that larger quantities of
then the cytosol, and finally the lysosomes and microsomes; Cr are required for beneficial effects on type 2 diabetics.
however, the complex has no propensity to bind to DNA. Significantly, the studies using >200-g Cr per day are
Kelley and coworkers have found that hepatocyte microsomes supported by studies on model rats.5456 Thus, continued
can catalytically modify the picolinate ligands, which would rat and human studies are required to further elucidate the
result in Cr release.46 potential use of Cr administration as an adjuvant therapy for
Isolated incidents of deleterious effects of [Cr(pic)3 ] type 2 diabetes.
supplementation have been reported.30 The nature of these The existence of a multinuclear CrIII carboxylate assembly
incidents makes their significance difficult to ascertain. In in an active biomolecule has spurred an interest in the
contrast, Anderson et al.47 fed rats diets containing up to synthesis and characterization of multinuclear oxo(hydroxo)-
100-mg Cr as [Cr(pic)3 ] per kg diet for 24 weeks; no acute bridged CrIII carboxylate assemblies.1 Well-characterized,
toxic effects were observed. No toxic effects of [Cr(pic)3 ] water-soluble assemblies have been tested for the ability
supplementation were noted in any of the studies from to stimulate insulin receptors tyrosine kinase ability in
the review articles mentioned previously, which combined a fashion similar to chromodulin. The trinuclear cation
monitored hundreds of subjects.1,30 No study has yet to +
[CrIII
3 O(O2 CCH2 CH3 )6 (H2 O)3 ] was found in vitro to mimic
examine the effects, positive or negative, of the long-term the ability of chromodulin to stimulate this activity.23 The
use of [Cr(pic)3 ]. Animal studies looking for DNA damage biomimetic cation remains intact after injection into the
and oxidative damage have started to appear. No effect on bloodstream and is taken up by cells intact.57,58 After 24 weeks
5-hydroxymethyl uracil levels have been observed in 10 obese of intravenous administration (0 20-g Cr/kg body mass) in
women who were given 400-g [Cr(pic)3 ] (50-g Cr) per healthy rats, the cation resulted in a concentration-dependent
day for 8 weeks.48 In contrast, rats given [Cr(pic)3 ] daily lowering of levels of fasting blood plasma LDL cholesterol,
by intravenous injection for 60 days have elevated levels of total cholesterol, triglycerides, and insulin and of two-hour
urinary 8-hydroxydeoxyguanosine and peroxidized lipids.49 plasma insulin and glucose levels after a glucose challenge.54
Potentially deleterious in vivo effects of [Cr(pic)3 ] have Zucker obese rats (a model of the early stages of type 2
recently been examined using Drosophila melanogaster.50 diabetes) after 24 weeks of supplementation (20g kg1 )
[Cr(pic)3 ], but not CrCl3 , at levels of 260-g Cr/kg food had lower fasting plasma total, HDL, and LDL cholesterol;
or less were found to lower the success rate of pupation and triglycerides; and insulin levels and lower two-hour plasma
eclosion and to arrest development of pupae in a concentration- insulin levels. The lowering of plasma insulin concentrations
dependent fashion. X-linked lethal analysis indicated that the with little effect on glucose concentrations suggests that the
supplement greatly enhances the rate of appearance of lethal cation increases insulin sensitivity.
mutations and of dominant female sterility.
6 CHROMATE TOXICITY
5 CHROMIUM THERAPEUTIC AGENTS AND
TYPE 2 DIABETES
Given its similarity to HPO4 2 and SO4 2 , chromate,
While Cr supplementation of the diet of healthy humans [CrVI O4 ]2 , is able to travel via nonspecific anion transporters
appears to have no statistically significant effects, the effects across the plasma membrane. Once inside a cell, cellular
of Cr on type 2 diabetic subjects are still an area of debate. enzymatic and other systems are capable of reducing the
The administration of pharmacological, rather than nutritional, chromate to CrV , CrIV , and CrIII species, which are generally
amounts of Cr could potentially result in beneficial effects, nondiffusing and thus trapped inside the cells. The mechanisms
especially for subjects with altered metabolisms that could of these processes have been a subject of intense research59,60
potentially lead to altered Cr status. A recent meta-analysis as they are directly related to the carcinogenicity and
of studies with diabetic subjects revealed that the combined mutagenicity of CrVI (recently brought to public attention
data from all placebo-controlled studies but one, the largest by the movie Erin Brockovich). CrVI is a potent carcinogen
study, indicated no effect from Cr administration.35 The when inhaled, although the potential carcinogenicity when
largest study by Anderson and coworkers gave 155 subjects taken orally is currently actively debated. In cells, cysteine,
in China 0-, 200-, or 1000-g Cr daily for 4 months.51 At glutathione, and ascorbate are probably significant players in
the highest Cr dosage, subjects had reduced fasting serum chromate reduction. Most recent studies have focused on CrV
glucose, insulin, and total cholesterol and lower 2-h insulin and as the species primarily responsible for carcinogenic effects.
glucose concentrations after a glucose challenge. Subjects also The involvement of CrV carbohydrate complexes in chromate-
possessed lower HbA1c levels. Anderson has reviewed studies derived DNA damage has been proposed;60 however, further
on the effects of Cr administration on type 2 diabetics;52,53 research is required to establish their significance. The ultimate
only studies using 200-g Cr daily reported no effects reduction product, CrIII , accumulates in the nucleus of cells and
CHROMIUM: BIOLOGICAL RELEVANCE 5
may form DNA protein and other cross-links; the deleterious 22. B. J. Clodfelder, J. Emamaullee, D. D. D. Hepburn, N. E.
potential of these cross-links is uncertain. Chakov, H. S. Nettles, and J. B. Vincent, J. Biol. Inorg. Chem.,
2001, 6, 608.
23. C. M. Davis, A. C. Royer, and J. B. Vincent, Inorg. Chem.,
1997, 36, 5316.
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25. J. B. Vincent, J. Nutr., 2000, 130, 715.
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Nutritional Aspects of Metals & Trace Elements. 257, 1251.
27. G. W. Evans, Int. J. Biosoc. Med. Res., 1989, 11, 163.
28. F. Mirasol, Chem. Market Rep. 2000, 257, 2000.
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12. A. Yamamoto, O. Wada, and T. Ono, Eur. J. Biochem., 1987, Chem. Res. Toxicol., 1999, 12, 483.
165, 627.
43. J. K. Speetjens, A. Parand, M. W. Crowder, J. B. Vincent, and
13. J. B. Vincent, J. Nutr., 1994, 124, 117. S. A. Woski, Polyhedron, 1999, 18, 2617.
14. A. Yamamoto, O. Wada, and S. Manabe, Biochem. Biophys. 44. K. D. Sugden, R. D. Geer, and S. G. Rogers, Biochemistry,
Res. Commun., 1989, 163, 89. 1992, 31, 11626.
15. Y. Sun, J. Ramirez, S. A. Woski, and J. B. Vincent, J. Biol. 45. D. D. D. Hepburn and J. B. Vincent, J. Inorg. Biochem., 2003,
Inorg. Chem., 2000, 5, 129. 94, 86.
16. C. M. Davis and J. B. Vincent, Arch. Biochem. Biophys., 1997, 46. S. A. Kareus, C. Kelley, H. S. Walton, and P. C. Sinclair, J.
339, 335. Hazard. Mater., 2001, B84, 163.
17. L. Jacquamet, Y. Sun, J. Hatfield, W. Gu, S. P. Cramer, 47. R. A. Anderson, N. A. Bryden, and M. M. Polansky, J. Am.
G. A. Lorigan, J. B. Vincent, and J.-M. Latour, J. Am. Chem. Coll. Nutr., 1997, 16, 273.
Soc., 2003, 125, 774.
48. I. Kato, J. H. Vogelman, V. Dilman, J. Karkoszka, K. Frenkel,
18. C. M. Davis and J. B. Vincent, Biochemistry, 1997, 36, 4382. N. P. Durr, N. Orentreich, and P. Toniolo, Eur. J. Epidemiol.,
19. C. M. Davis, K. H. Sumrall, and J. B. Vincent, Biochemistry, 1998, 14, 621.
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20. K. H. Sumrall and J. B. Vincent, Polyhedron, 1997, 16, 4171. Polyhedron, 2003, 22, 455.
21. A. Yamamoto, O. Wada, and T. Ono, J. Inorg. Biochem., 1984, 50. D. D. D. Hepburn, J. Xiao, S. Bindom, J. B. Vincent, and
22, 91. J. ODonnell, Proc. Natl. Acad. Sci. U.S.A., 2003, 100, 3766.
6 CHROMIUM: BIOLOGICAL RELEVANCE
51. R. A. Anderson, N. C. Cheng, N. A. Bryden, M. M. 56. W. T. Cefalu, Z. Q. Wang, X. H. Zhang, L. C. Baldor, and
Polansky, N. Cheng, J. Chi, and J. Feng, Diabetes, 1997, 46, J. C. Russell, J. Nutr., 2002, 132, 1107.
1786. 57. A. A. Shute and J. B. Vincent, J. Inorg. Biochem., 2002, 89,
52. R. A. Anderson, J. Am. Coll. Nutr., 1998, 17, 548. 272.
53. R. A. Anderson, Diabetes Metab. (Paris), 2000, 26, 22. 58. A. A. Shute and J. B. Vincent, Polyhedron, 2001, 20, 2241.
54. Y. Sun, B. J. Clodfelder, A. A. Shute, T. Irvin, and J. B. Vincent, 59. A. Levina, R. Codd, C. T. Dillion, and P. A. Lay, Prog. Inorg.
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55. Y. Sun, K. Mallya, J. Ramirez, and J. B. Vincent, J. Biol. Inorg. 60. R. Codd, C. T. Dillion, A. Levina, and P. A. Lay, Coord. Chem.
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Chromium: Inorganic & by its importance in catalytic processes (notably ethylene
polymerization).
Coordination Chemistry
Klaus H. Theopold 2 THE ELEMENT
University of Delaware, Newark, DE, USA
2.1 Occurrence
The only chromium ore of practical importance is chromite,
a black spinel of the idealized composition FeCr2 O4 ; in
1 Introduction 1
practice, it contains varying amounts of MgO, Al2 O3 , and
2 The Element 1
SiO2 . Major producers of chromite include South Africa,
3 Binary Compounds and Simple Salts 3
Kazakhstan, India, and Turkey. Since 1900, the production
4 Coordination Compounds 5
of chromite has doubled roughly every decade, reaching an
5 Cr Cr Bonds 12
estimated 14.2 million tons in 1998. Chromium is more
6 Related Articles 13
rarely found as the mineral crocoite (PbCrO4 ) and minor
7 References 13
amounts of the element occur in many other minerals.
Traces of chromium ions are responsible for the color of
emeralds (Be3 Al2 Si6 O18 ) and rubies (Al2 O3 ). At an average
Abbreviations concentration of 100 ppm in the earths crust, chromium ranks
21st in elemental abundance; its typical level in seawater is
mhp = deprotonated 6-methyl-2-hydroxypyridine; THT = ca. 2 104 ppm.
tetrahydrothiophene.
2.2 Production and Uses4
The greater part (ca. 85%) of chromite ore production is
reduced by heating with coal to give ferrochrome, used in
1 INTRODUCTION the manufacture of alloy steels. Pure chromium metal for
use in iron-free alloys and metal-containing ceramics is pro-
The transition metal chromium has played a prominent duced by reduction of Cr2 O3 . Common reducing agents are
role in the development of inorganic chemistry. Discovered aluminum, carbon, or silicon. Another process involves the
in 1797 by the French chemist Louis N. Vauquelin in electrolysis of chrome alum (NH4 Cr(SO4 )2 12H2 O) solutions.
the rare mineral crocoite (PbCrO4 ), it was named for the CrO3 solutions are employed in electroplating of chromium
varied colors of its compounds (chroma () = color). on other metals to impart wear resistance and for decorative
Chromium compounds exist in an unusually large number purposes.
of formal oxidation states (IV to +VI) (see Oxidation Less than 15% of the ore is transformed into
Number); however, only the +II to +VI states are accessible chromium compounds, principally chromates, dichromates,
in water. Hexavalent chromium is a powerful oxidant and chromium(VI) oxide, chromium(III) oxide, and so on. Alka-
the use of chromium-based oxidants in organic synthesis13 line oxidative roasting of chromite in rotary kilns yields
goes back well over a century (witness the Etard reaction of sodium chromate (see equation 1), which is leached out
alkylbenzenes with chromyl chloride (CrO2 Cl2 ), which was with water and typically converted into sodium dichro-
first described in 1880). Chromium(II), on the other hand, is mate with sulfuric acid (equation 2) or carbon diox-
strongly reducing, and by far the most stable oxidation state ide (equation 3). Further treatment of sodium dichromate
of the element is +III, giving rise to an extensive series of with sulfuric acid yields chromium(VI) oxide (chromic
stable inorganic compounds. acid), while its reduction (with carbon, sulfur, or ammo-
The remarkable chemical and configurational stability of nium salts) produces chromium(III) oxide. Finally, basic
octahedral CrIII complexes (see Octahedral) was responsible chromium(III) salts, for example Cr(OH)SO4 , which are
for their role in the groundbreaking work of Alfred used as tanning agents for animal hides, also result
Werner, the father of modern coordination chemistry (see from reduction of sodium dichromate. Heterogeneous
Coordination Chemistry: History). In the twentieth century, chromium catalysts are used for the polymerization of
the same properties led to their use in studies of the ethylene.
reaction mechanisms of metal complexes. In recent years, >1000 C
4FeCr2 O4 + 4Na2 CO3 + 7O2 8Na2 CrO4 + 2Fe2 O3 + 8O2 (1)
the chemistry of the chromium carbon bond has been the
most active area of research in chromium chemistry (see 2Na2 CrO4 + H2 SO4 Na2 Cr2 O7 + Na2 SO4 + H2 O (2)
Chromium: Organometallic Chemistry), motivated in part 2Na2 CrO4 + H2 O + 2CO2 Na2 Cr2 O7 + 2NaHCO3 (3)
2 CHROMIUM: INORGANIC & COORDINATION CHEMISTRY
2.3 Atomic Properties57 106 cm3 g1 (ambient temperature), and linear coefficient of
thermal expansion: 6.2 106 K1 .
Chromium has the atomic number 24. Of the 13
known isotopes (mass numbers 45 57), four are sta-
ble, giving chromium the relative atomic mass 51.9961
(12 C = 12.0000). Table 1 lists the properties of some 2.5 Chemical Properties
isotopes. 53 Cr may be used for NMR spectroscopy;8
however, its relative receptivity (8.62 105 , 1 H = 1.00), Chromium is fairly resistant to ordinary corrosive agents.
quadrupole moment (4.1 1030 m2 ), and low resonance However, at elevated temperatures it reacts with many
frequency (16.956 MHz, 1 H = 300 MHz) pose experimen- elements, including the halogens, oxygen and sulfur, nitrogen,
tal difficulties. Radioactive 51 Cr is used in medical tracer carbon, and boron. It dissolves readily in dilute HCl or H2 SO4 ,
studies. but not in nitric acid, phosphoric acid, or even aqua regia. The
Chromium atoms have the ground-state electronic con- oxidizing acids are thought to passivate the metal surface
figuration [Ar]3d5 4s1 , giving rise to the term symbol 7 S3 . by formation of a thin protective oxide layer. Under certain
Its Electron Affinity is 64.3 kJ mol1 (0.67 eV) and its first conditions, this passivation layer may be formed and destroyed
through sixth ionization potentials are 652.7 (6.764), 1592 periodically, leading to oscillations in the hydrogen evolution
(16.50), 2987 (30.95), 4740 (49.12), 6690 (69.33), and upon dissolution of the metal. Nonpassivated chromium is a
8738 (90.55) kJ mol1 (eV), respectively (see Ionization strong reducing agent; see equations (4) and (5).
Potential).
Cr2+ (aq) + 2e
Cr(s) E = 0.91 V (4)
2.4 Physical Properties
Cr (aq) + 3e Cr(s)
3+
E = 0.74 V (5)
Solid chromium adopts a body-centered cubic structure
and crystallizes in the space group Im3m with a =
288.46 pm; its density is 7.19 g cm3 (at 293 K). The The most common oxidation states of chromium in
metal melts at 2130 (20) K and boils at 2945 K; the inorganic compounds are +II, +III, and +VI. By comparison,
corresponding enthalpies are Hfusion = 15.3 kJ mol1 and there are few stable compounds of tetravalent or pentavalent
Hvap = 348.78 kJ mol1 . Values of various thermodynamic chromium; these oxidation states are largely represented by
functions are listed in Table 2. Some other values are: thermal reactive intermediates in redox reactions. -Acid ligands like
conductivity: 93.7 W m1 K1 (at 300 K), electrical resistivity: CO (see -Acid Ligand) stabilize chromium in very low formal
12.7 108 m (at 273 K), magnetic susceptibility: +3.5 oxidation states (down to IV!). Table 3 lists oxidations states
and coordination environments for representative chromium
Table 1 Properties of chromium isotopes compounds.
Coordination
Oxidation state number Coordination geometry Examples
3 BINARY COMPOUNDS AND SIMPLE SALTS they exhibit electrical conductivity. They are resistant to
chemical attack.
Chromium carbides have been produced by melting
3.1 Hydrides mixtures of chromium and graphite under vacuum or by
heating Cr2 O3 with C. Chromium metal reacts with CH4
The solubility of hydrogen in chromium metal increases at 600 800 C, forming carbides and H2 . Three different
with temperature. The existence of two discrete hydrides of compounds have been identified, namely, Cr23 C6 , Cr7 C3 ,
stoichiometry CrH and CrH2 with different structures had been and Cr3 C2 (see Carbides: Transition Metal Solid-state
suggested in the older literature; however, the existence of the Chemistry). They are very hard and high melting.
latter was called into question. Recent experiments involving Chromium silicides have been isolated, inter alia, from
the reaction of Cr atoms with H2 and Matrix Isolation of melts of chromium/silicon mixtures, from the reduction of
the products have provided spectroscopic evidence for the Cr2 O3 /SiO2 mixtures (e.g. with Al), and from the electrolysis
molecules CrH and CrH2 . Species with higher hydrogen of Na2 SiF6 /CrF2 melts. Tentatively identified compounds
content are now thought to be dihydrogen complexes, for include Cr3 Si, Cr2 Si, Cr5 Si3 , Cr3 Si2 , CrSi, and CrSi2 . All
example, (H2 )CrH, (H2 )CrH2 , and (H2 )2 CrH2 .12 of these appear metallic and conduct electricity. They are hard
and brittle, have high melting points, and are resistant to attack
by acids.
3.2 Compounds with Elements of Groups 1315 Chromium nitrides have been prepared by several routes:
heating of chromium metal in N2 , reaction of chromium
Chromium borides have been prepared by heating mixtures borides with NH3 , and heating of CrCl3 in gaseous NH3 .
of chromium and boron or Cr2 O3 and boron; another The two stable nitrides have the composition Cr2 N and CrN
preparation employed electrolysis of molten oxides of both (see Nitrides: Transition Metal Solid-state Chemistry). At
elements. A number of phases have been identified; their very high temperatures, both decompose into the constituent
compositions are Cr4 B, Cr2 B, Cr5 B3 , CrB, Cr2 B3 , Cr3 B4 , elements (CrN, >1425 C; Cr2 N, >700 C). CrN is very stable
and CrB2 (see Borides: Solid-state Chemistry).13 Crystals of chemically, while Cr2 N dissolves in dilute acid with liberation
several phases have been grown from high-temperature Al of H2 .
solutions.14 The chromium borides are refractory materials The chromium phosphides Cr3 P, Cr2 P, CrP, Cr2 P3 , and
with high melting points and metallic character, for example, CrP2 have been described in the literature (see Phosphides:
4 CHROMIUM: INORGANIC & COORDINATION CHEMISTRY
Solid-state Chemistry). They were prepared by direct reaction to its smaller size, favoring four over six coordination,
of the elements. and to the relative strength of the Cr=O multiple bond.
Acidic dichromate solutions are strongly oxidizing. The
nonhygroscopic K2 Cr2 O7 has been used extensively as a
3.3 Oxides and Sulfides standard reagent in redox titrations.
Of the chromium oxides, only Cr2 O3 , CrO2 , and CrO3 are
2
of significance. 2
O O 126o
O
163 pm
Chromium(III) oxide (Cr2 O3 ) is produced commercially 166 pm
Cr + 2H+ O Cr O Cr O
+ H2O
by reduction of CrO3 . Other preparations include burning O O O O
O 179 pm
of chromium metal in O2 , thermal decomposition of
CrO3 or (NH4 )2 Cr2 O7 , and heating of the hydrous oxide (1) (2)
(Cr2 O3 nH2 O) obtained by adding hydroxide to aqueous (6)
solutions of CrIII ion. When prepared in the latter way, it
is reactive and amphoteric (see Amphoterism); dissolution in Reduction of CrO4 2 (chromates(VI)) yields CrO4 3 ions
acid reforms the purple [Cr(OH2 )6 ]3+ ion (CrIII (aq)), while (chromates(V)), which can be isolated in the form of their
treatment with base yields dark green chromite solutions, alkali metal and alkaline-earth metal salts, for example,
that is [Cr(OH)6 ]3 . Cr2 O3 is a green solid, which begins to Na3 CrO4 and Ba3 (CrO4 )2 . The black or blue paramagnetic
decompose before it reaches its melting point (ca. 2435 C). salts contain isolated CrO4 tetrahedra and are hygroscopic;
It adopts the corundum structure, that is, a hexagonally close- upon dissolution in water they disproportionate to CrIII and
packed array of oxide ions with two-thirds of the octahedral CrVI .
holes occupied by CrIII ions (see Close Packing). It is a Further reduction produces CrO4 4 , an isolated tetrahedral
semiconductor (conductivity: 106 107 1 cm1 ) and an anion found for example in the deep green Na4 CrO4 . The
antiferromagnet with a Neel temperature of ca. 50 C. d2 configuration of the CrIV ion gives rise to Paramagnetism
Chromium(IV) oxide (CrO2 ) is formed as an intermediate consistent with two unpaired electrons.
in the thermal decomposition of CrO3 . It is commercially The sulfide ion stabilizes chromium in its lower oxidation
prepared by hydrothermal treatment (T = 250 500 C, P = states. Thus, both Cr2 S3 and CrS exist, but a chromium(VI)
50 3000 atm) of CrO3 . CrO2 is a brown black solid that trisulfide does not. Heating of Cr2 S3 causes decomposition,
decomposes to Cr2 O3 upon heating to 250 500 C. It has the leading to CrS by way of a number of phases of intermediate
rutile structure (slightly distorted hexagonal close packing of composition. Both Cr2 S3 and CrS are semiconductors and
oxide ions with one half of the octahedral holes filled by CrIV exhibit magnetic ordering; some of the other sulfides exhibit
ions). It exhibits metallic conductance and is ferromagnetic metallic character.
(see Ferromagnetism); the latter property leads to its use in Several selenides and tellurides of chromium are also
magnetic recording tapes. known; their stoichiometries parallel those of the sulfides.
Chromium(VI) oxide (CrO3 , chromic acid) is made by
treatment of dichromate (e.g. Na2 Cr2 O7 ) with sulfuric acid. It
is an orange red solid with a melting point of only 197 C. 3.4 Halides and Oxyhalides
Upon heating it slowly loses oxygen, eventually yielding
The known halides of chromium are listed in Table 4
Cr2 O3 . The structure of the rather covalent oxide consists of
with some of their physical properties. The instability of
chains of corner-sharing tetrahedra (see Tetrahedral). CrO3
a hexavalent chromium halide is noteworthy. The higher
reacts vigorously with organic substances; it is widely used as
halides are prepared by direct reaction of the metal with the
an oxidant in synthetic organic chemistry.1,2
CrO3 dissolves in base, forming yellow solutions of the
tetrahedral chromate ion (CrO4 2 ) (1). Chromate is a weak Table 4 Chromium halides
base; upon lowering of the pH it forms HCrO4 (pKa 6.49)
Fluorides Chlorides Bromides Iodides
and eventually H2 CrO4 (pKa 0.74). The latter species are in
equilibrium with the orange dichromate ion (Cr2 O7 2 ) (2) CrF6 ?
(equation 6). In strongly acidic media, further polymerization CrF5 red,
yields tri- and tetrachromates (Cr3 O10 2 and Cr4 O13 2 ), short mp 30 C
CrF4 colorless, CrCl4 gas CrBr4 gas
chains of corner-sharing tetrahedra anticipating the structure mp 277 C phase only phase only
of the end member CrO3 . A comparison of structural data CrF3 green, CrCl3 violet, CrBr3 dark CrI3 black,
for a series of mono- and polychromates showed a smooth mp 1404 C mp 1150 C green, mp >600 C
correlation of the CrO distances with increasing degree of mp 1130 C
polymerization.15 By comparison with the heavier Group CrF2 green, CrCl2 white, CrBr2 white, CrI2
mp 894 C mp 824 C mp 842 C red brown,
6 elements (Mo, W), chromium shows little tendency for mp 868 C
the formation of Polyoxometalates. This is probably due
CHROMIUM: INORGANIC & COORDINATION CHEMISTRY 5
appropriate halogen. The chromium(II) halides are obtained Table 5 Oxyhalides of chromium
by reduction of the trihalides with H2 or by heating of the
metal with HX. Fluorides Chlorides Bromides
A volatile yellow compound of the composition CrF6 has CrOF4
been reported; however, those claims have been disputed.16 red, mp 55 C
Recent computational studies tend toward supporting the exis- CrO2 F2 CrO2 Cl2 CrO2 Br2
violet, mp 32 C red, mp 96.5 C, red
tence of the hexafluoride,17 but definitive experimental work bp 117 C
is still missing. Treatment of chromium with fluorine yields CrOF3 CrOCl3
CrF5 , even at high temperatures (400 C). CrF5 is a sticky purple, dec. 500 C dark red
red solid with a vapor pressure of 3.3 mbar (330 Pa) at 20 C. CrOF2
Gaseous CrF5 is yellow and exhibits no tendency toward dis- brown black
proportionation up to 100 C. It reacts rapidly with moisture,
producing among others CrOF4 and CrO2 F2 . The molecular
structure of CrF5 is a distorted trigonal bipyramid. In the solid bromides and iodides parallel those of the corresponding
state, it polymerizes by formation of fluoride bridges. CrF4 chlorides.
has been prepared by fluorination of Cr, CrF3 , or CrCl3 , and The known oxyhalides of chromium are listed in Table 5
by reaction of CrF5 with Cl2 . It has been described as brown, with some of their physical properties.20 Only chromyl
dark green, bluish, and finally colorless (in a Ne matrix). In chloride (CrO2 Cl2 ) (3) is of practical importance. The red
the gas phase, it adopts a regular tetrahedral structure (CrF, liquid is prepared by treatment of CrO3 with HCl or by
170.6(2) pm).18 CrF3 is a nonvolatile green solid, which is heating a mixture of K2 Cr2 O7 and KCl with concentrated
best prepared by the reaction of CrCl3 with HF at 500 C. Its H2 SO4 (the latter reaction is the basis for a qualitative test
structure consists of hexagonally close-packed fluoride ions for chloride). Chlorochromic acid (CrO2 (OH)Cl) is formed
with chromium in octahedral coordination. Light green CrF2 as an intermediate in these reactions; its salts can be isolated
may be prepared by reduction of CrF3 with hydrogen at 400 C as crystalline solids. Chromyl chloride is light sensitive and,
or by treatment of CrCl2 with HF. It features a Jahn Teller like all oxyhalides of chromium, easily hydrolyzed by water.
distorted rutile structure with chromium fluorine distances of It is also an extremely strong oxidant, reacting vigorously
200 and 243 pm. with many organic compounds. It adopts a pseudo-tetrahedral
The chromium chloride in the highest oxidation state is structure, with the OCrO angle (108.5 ) being smaller than
CrCl4 . This is not a stable compound under ordinary con- the ClCrCl angle (113 ). The latter fact is in contradiction
to the tenets of valence shell electron pair repulsion (VSEPR)
ditions; however, it may be produced by evaporation of
theory. Numerous derivatives of chromyl chloride of the type
anhydrous CrCl3 at ca. 560 C and trapped in an argon matrix.
CrO2 X2 (X = NO3 , ClO4 , OAc, OR, N3 , etc.) are known. The
Its IR spectrum indicates a tetrahedral structure. Further heat-
electronic and vibrational spectroscopy of CrVI compounds,
ing of CrCl3 yields molecular CrCl3 at ca. 600 C (trigonal
and chromyl derivatives in particular, has been reviewed.21
planar) and finally CrCl2 molecules at 780 C (linear).19 Prob-
ably the most important chromium halide is the violet CrCl3 ,
the starting material for much of synthetic chromium chem- 108.5o
istry. In the solid state, it adopts an unusual layered structure O O
consisting of a cubic close packing of chloride ions with 158 pm Cr
213 pm
two-thirds of the octahedral holes adjacent to every other Cl Cl
anion layer occupied by chromium atoms. Pure CrCl3 does (3)
not dissolve in water. However, addition of traces of reducing
agents or CrII results in ready dissolution; this is thought to be
due to electron transfer catalysis, that is, reduction of substi-
tutionally inert CrIII on the crystal surface to labile CrII , which
readily dissolves and, in turn, functions as a reducing agent 4 COORDINATION COMPOUNDS
for further CrIII . The same effect is used to practical advantage
in the preparation of CrCl3 (THF)3 , a useful precursor for 4.1 Overview
organometallic chromium compounds, which is prepared by
Soxhlet extraction of CrCl3 (with a little Zn metal added) with Chromium complexes exist in a very wide range of formal
tetrahydrofuran (THF). Treatment of Cr metal with HCl or H2 oxidation states (IV to +VI). The extremely low ones are
reduction of CrCl3 (both at ca. 600 C) yields colorless CrCl2 . stabilized by -acid ligands, notably carbon monoxide; these
The dichloride readily dissolves in water, yielding dark blue are described in the article on organometallic compounds (see
solutions of the strongly reducing Cr2+ (aq) ion. Chromium: Organometallic Chemistry). The extensive coor-
Like the tetrachloride, CrBr4 exists only in the gas phase. dination chemistry of CrII spans coordination numbers 3 7,
CrI4 is not known. The structures and properties of the lower but is dominated by octahedral complexes. Complexes of
6 CHROMIUM: INORGANIC & COORDINATION CHEMISTRY
divalent chromium are usually strongly reducing and are often the fluorophosphine complexes Cr(PF3 )6 and Cr[(PF2 )2 NR]3 .
susceptible to air oxidation. By far the largest number of coor- The phosphine complexes are all diamagnetic and colorless or
dination compounds of chromium exists in the +III oxidation yellow, indicating large ligand field splittings.
state. Commonly octahedral, they are substitution inert and
often easily synthesized. In mononuclear complexes, the d3
electronic configuration (t2g 3 ) gives rise to spin-only magnetic N
moments (3.87 B ), but in polynuclear complexes, antiferro- N
magnetic coupling between the CrIII ions results in lower val- P Cr P
ues (see Magnetism of Transition Metal Ions). The electronic P P
spectra and the photochemistry of trivalent chromium have N
been studied extensively. The oxidation states +IV and +V N
have attracted some attention recently. However, these oxida- (4)
tion states must still be considered unusual in the context of
chromium chemistry. Finally, CrVI is a common and important
oxidation state of this element, although the number of coordi- There are Cr0 and CrI complexes of both aryl and alkyl
nation compounds representing it is rather limited. The notion isocyanides (RNC) as well as cyanides; because of their
of a true Cr6+ ion is, of course, unrealistic, and the chemistry CrC linkages, these are described elsewhere (see Chromium:
of CrVI is marked by strong Covalent Bonds to oxygen and Organometallic Chemistry).
halogens. These compounds are strong oxidants. By compar-
ison to the heavier elements in group 6 (Mo, W), chromium
shows much less tendency toward Cluster formation. 4.3 Oxidation State II
A comprehensive treatise of the coordination chemistry of
chromium22 is available. The coordination chemistry of CrII can be subdivided into
the realm of mononuclear coordination compounds, which can
be derived (at least formally) from the blue [Cr(OH2 )6 ]2+ ion,
4.2 Oxidation States 0 and I and the chemistry of metal metal bonded species (analogs
of Cr2 (OAc)4 ). Most of the former are octahedral high-
Reduction of common chromium salts (CrCl3 , CrCl2 , spin complexes with distinct tetragonal distortions caused
Cr2 (OAc)4 ) in the presence of chelating nitrogen heterocycles by the Jahn Teller Effect. With strong-field ligands, low-spin
like bipy and phen provides access to formally neutral Cr0 octahedral complexes are formed, and there are also some four-
complexes Cr(LL)3 as well as salts of the type [Cr(LL)3 ]X coordinate complexes of various coordination geometries. The
(LL = bipy, phen; X = I, ClO4 ). [Cr(bipy)3 ] is a black solid; metal metal bonded species are described in Section 5.
its molecular structure is a trigonally distorted octahedron
(CrN, 208 pm; NCrN, 74.7 ). Owing to the high ligand
field strength of the nitrogen ligands, and as shown by 4.3.1 Hydride and Halide Ligands
their Diamagnetism, the Cr(LL)3 complexes adopt low-spin
configurations (t2g 6 ) (see High-spin & Low-spin Compounds). CrII hydrides without CrC bonds are restricted to the
[Cr(bipy)3 ]X has an effective magnetic moment of 2.07 B , seven-coordinate [H2 Cr{P(OMe)3 }5 ] and [HCr{(Me2 PCH2 )3 -
consistent with one unpaired electron (t2g 5 ). In solution, it CMe}2 ]+ BEt4 . The former complex results from oxidative
exhibits an electron spin resonance (ESR) spectrum at g = addition of H2 to [Cr{P(OMe)3 }6 ], while the latter was isolated
1.9971 with hyperfine splitting to both 53 Cr and 14 N evident. from a reaction of [CrCl3 {(Me2 PCH2 )3 CMe}] with LiHBEt3 .
Electrochemical experiments in aprotic solvents (MeCN) Both are diamagnetic molecules and their NMR spectra
show reversible redox processes involving [Cr(LL)3 ] ions indicate fluxional behavior (see Fluxional Molecule).
containing chromium in the oxidation states I, 0, I, II, and The anhydrous halides CrX2 (X = F, Cl, Br, I) were
III. The half-wave potential for the [Cr(bipy)3 ]+ /Cr(bipy)3 described earlier (Section 3.4). Through formal addition
couple lies at 1.28 V versus the Ag/AgCl electrode. of halide ions, various halochromates(II) can be formed.
Highly reduced chromium binds dinitrogen, for example These feature complex ions of the types CrX3 , CrX4 2 ,
in trans-[Cr(dmpe)2 (N2 )2 ] (4). Its crystal structure shows CrX5 3 , and CrX6 4 . These, when they contain fluoride
linearly bound N2 ligands (CrN, 187.4 pm, NN, 112.2 pm) ion, are, for example, the light blue MCrF3 (M = Na, K,
and relatively short CrP distances (CrPav , 229.6 pm). Rb, NH4 ), dark blue Na2 CrF4 , or MCrF4 (M = Ca, Sr,
The related Cr(dmpe)3 exhibits similarly short CrP bonds Ba), and Ba2 CrF6 . Most of these compounds contain six-
(231.7 pm). These short CrP distances are thought to be coordinate CrII . All are more or less paramagnetic, because
due to Back Bonding to the phosphine ligand. Both of the high-spin d4 configuration (t2g 3 eg 1 ); thus KCrF3
Cr(dmpe)3 and Cr[P(OMe)3 ]6 were prepared by metal vapor has eff = 4.9 B and Na2 CrF4 has eff = 4.8 B . There
synthesis (see Metal Vapor Synthesis of Transition Metal is evidence for magnetic coupling at low temperatures.
Compounds). The same technique may also be used to prepare Among the corresponding chloro- and bromochromates(II),
CHROMIUM: INORGANIC & COORDINATION CHEMISTRY 7
the tetrahalochromates M2 CrX4 (M = alkali metal, organic those of primary alcohols are insoluble polymers. The wide
cations; X = Cl, Br) especially have been the subject of variety of substituents gives rise to considerable structural
detailed structural and magnetic studies, because some of complexity. In donor solvents such as THF, solvent adducts
these materials show weak ferromagnetic coupling. While of the type [Cr(OR)2 (THF)2 ] are formed. They probably
the overwhelming majority of magnetically coupled transition adopt square-planar geometries with trans-OR groups, as has
metal complexes exhibit Antiferromagnetism, ferromagnetic been shown for [(2,6-(t-Bu)2 -4-MeC6 H2 O)Cr(THF)2 ].23 The
coupling is rare and of great interest for the preparation of complex [Li(THF)2 ] [Cr{OC(t-Bu)3 }2 Cl] features an unusual
novel magnetic materials (see Magnetism of Extended Arrays T-shaped geometry (6).
in Inorganic Solids).
The colorless alkali metal salts adopt a distorted K2 NiF4
structure, containing layers of tetragonally distorted CrCl6 C(t-Bu)3
octahedra held together by the M+ ions. At room temperature Cl O 188 pm
their effective magnetic moments slightly exceed the spin- THF Li Cr
THF 158o
only values; upon lowering the temperature, they rise O
199 pm
(to ca. 9 B per Cr atom at 90 K). Curie temperatures C(t-Bu)3
between 40 and 75 K have been found. Some of the
(6)
tetrahalochromates(II) are antiferromagnets. For example, the
structure of [NMe2 H2 ]2 [CrCl4 ] contains isolated [Cr3 Cl12 ]6
units (5) in which three distorted CrCl6 octahedra are joined
Cr(acac)2 is a yellow paramagnetic solid with an effective
via shared trigonal faces to form a linear chain of three
magnetic moment (4.99 B ), consistent with a high-spin d4
chromium atoms.
electronic configuration. Its crystal structure shows chromium
coordinated by four oxygen atoms in a plane (CrOav , 198 pm)
6 and two long intermolecular contacts between the metal atom
Cl Cl Cl Cl
Cl Cl and the methine carbons of neighboring molecules (CrC,
Cr Cr Cr Cl
Cl Cl 305 pm), giving chromium a severely distorted octahedral
Cl Cl Cl
coordination environment. A few other -diketonates of CrII
(5) have been prepared.
A number of adducts of chromium(II) halides with oxygen-
containing donor molecules have been characterized. They
4.3.2 Oxygen and Sulfur Ligands have the composition CrX2 (L)2 , where X = Cl, Br, I and L =
THF, urea, biuret, dimethylsulfoxide (DMSO), phosphine
Solutions of the bright blue [Cr(OH2 )6 ]2+ ion can be oxide, arsine oxide, and so on. Most are blue high-spin
prepared by dissolution of pure chromium metal in mineral molecules (eff = 4.4 5.0 B ). Pale-green [CrCl2 (THF)2 ]
acids or by reduction of CrIII with exclusion of oxygen. CrII (aq) loses one equivalent of THF in vacuo, thereby yielding
is a strong reducing agent (see equation 4) and has long colorless [CrCl2 (THF)], which is a useful synthetic precursor
been used in mechanistic investigations of electron transfer for nonaqueous CrII chemistry.
reactions; more recently it has also found applications as a Sulfur-based CrII coordination compounds include a series
reducing agent in synthetic organic chemistry. Even in the of dithiocarbamates of the type [Cr(S2 CNR2 )2 ] (R = Me, Et
absence of O2 , aqueous CrII solutions slowly decompose or R2 = C4 H8 ), which are antiferromagnetically coupled. The
with liberation of H2 ; this reaction is catalyzed by various diethyl-substituted compound is an S-bridged dimer, making
impurities. The electronic spectrum of the [Cr(OH2 )6 ]2+ ion chromium five-coordinate. Square-planar CrII coordinated by
exhibits a broad asymmetric absorption at 14 000 cm1 and sulfur occurs in the violet [NEt4 ]2 [Cr(S2 C2 H4 )2 ]. Finally,
a weaker shoulder at 9500 cm1 , features that are consistent Thiourea and its derivatives form adducts with CrII halides,
with a tetragonally distorted octahedral complex. While the which are similar to the adducts with O-donors mentioned
crystal structure of the [Cr(OH2 )6 ]2+ ion is not known, the above.
structure of the closely related Cr(OH2 )4 (SO4 ) has been
determined. The complex features trans sulfato oxygens with
rather long bond distances (CrO, 242 246 pm) and four 4.3.3 Nitrogen and Phosphorus Ligands
equatorial water oxygens with normal bond distances (CrO,
203 205 pm). This tetragonal elongation is the expected Ammonia deprotonates [Cr(OH2 )6 ]2+ , resulting in pre-
Jahn Teller distortion. cipitation of brown CrII hydroxide. However, treatment of
CrII alkoxides [Cr(OR)2 ] are conveniently prepared solid halides CrX2 or ethanol solutions of hydrated CrX2
by alcoholysis of chromium amides, for example with NH3 gas yields blue diammines [Cr(NH3 )2 X2 ], violet
[Cr{N(SiMe3 )2 }2 (THF)2 ]. The alkoxides with bulky pentammines [Cr(NH3 )5 X]X, and greenish-gray hexammines
substituents are appreciably soluble in organic solvents, but [Cr(NH3 )6 ]X2 . Their magnetic behavior is that expected of
8 CHROMIUM: INORGANIC & COORDINATION CHEMISTRY
high-spin complexes. Spectroscopic measurements and com- [Cr{N(CH2 CH2 PR2 )}X]+ (R = Cy, Ph), and the N analogs
parative X-ray powder diffraction studies are consistent with [Cr{N(CH2 CH2 NR2 )}X]+ (R = Me, Et). These complexes
Jahn Teller distorted octahedral structures. are thought to adopt trigonal bipyramidal structures in which
Substitution of various chelating bi- and polydentate the coordinated halide occupies an axial position.
amines, for example, en, 1,3-diaminopropane, dien, trien,
and so on, in nonaqueous media yields an extensive series of
octahedral amine complexes, which range in color from blue to 4.4 Oxidation State III
purple. Their effective magnetic moments (4.7 4.9 B ) and
electronic spectra are best explained assuming tetragonally Central to the coordination chemistry of CrIII is six
distorted octahedral geometries. coordination in an essentially octahedral arrangement of
Nitrogen heterocycles, either monodentate or incorporated ligands, because of the large ligand field stabilization energy
into chelating ligands, form many CrII complexes. Most com- of the d3 configuration in this geometry. There are thousands
mon among these are compounds containing pyridine and of mononuclear CrIII complexes, which exhibit effective
its derivatives. Complexes of the types [Cr(py)4 X2 ] and magnetic moments close to or slightly below the spin-only
[Cr(py)6 ]X2 are all high spin and their spectra show the value (S = 3/2, 3.88 B ). There are also a large number
usual pattern of distorted octahedral coordination of CrII . of CrIII Polynuclear Complexes, for example those with
Analogous complexes have been prepared with pyrazoles bridging hydroxide ligands, in which exchange coupling of
and imidazoles. With the introduction of bidentate hetero- the spins results in lower moments. The electronic spectra
cyclic ligands (bipy, phen, etc.), the spin state eventually of CrIII complexes are well understood. Consultation of
changes to low spin. Thus halide-bridged [Cr(bipy)Cl2 ] is the corresponding Tanabe Sugano Diagram predicts three
high spin, but [Cr(bipy)2 Cl2 ] and [Cr(bipy)3 ]Cl2 are low- spin-allowed transitions, namely, 4 A2g 4
T2g (F), 4 A2g
4 4 4
spin complexes (t2g 4 , eff = 3.0 B ). Polypyrazolylborate T1g (F), and A2g T1g (P), and three bands have indeed
ligands (also called scorpionates) have attracted increas- been found for many complexes. The lowest energy transition
ing attention recently.24 CrII complexes of such ligands is a direct measure of the ligand field splitting (10 Dq or
include [Cr(HBpz3 )2 ] and [Cr(Bpz4 )2 ], which are both 0 ); for the [Cr(OH2 )6 ]3+ ion, this transition lies at ca.
high-spin, distorted octahedral complexes. More sterically 18 000 cm1 . The photochemistry of CrIII complexes has been
hindered tris(pyrazolyl)borates facilitate isolation of four- studied in some detail and a recent review is available.26
coordinate (e.g. cis-divacant octahedral TptBu,Me CrCl) and The reactivity of CrIII complexes is marked by very
five-coordinate (e.g. trigonal bipyramidal TptBu,Me Cr(L)Cl) slow Ligand Substitution reactions, resulting in unusual
complexes. Use of bidentate pyrazolylborates, as in configurational stability. Many chiral complexes have been
[Cr(H2 Bpz2 )2 ] and [Cr(Et2 Bpz2 )2 ], yields square-planar CrII resolved. There has been a recent resurgence of interest in
complexes, for example (7). organochromium(III) complexes, owing to the importance
of chromium in catalytic processes (see Chromium:
Organometallic Chemistry).
out on the basis of spectroscopic and structural evidence. of isomers by gas chromatography and for gas-phase structure
The chromium atoms are displaced from the centers of the determinations by electron diffraction. Owing to its stability
octahedra formed by the halide ions, such that the CrCr and solubility in organic solvents, paramagnetic [Cr(acac)3 ]
distance is increased. The interactions of adjacent CrIII ions has been used as a relaxation agent in 13 C NMR spectroscopy.
have indeed been called repulsive. This is in contrast to the Electrophilic substitutions at the coordinated diketonato ring
isostructural Mo and W compounds, which show evidence for are facile, and this has been taken as an evidence of an aromatic
metal metal bonding. nature.
Attempts to prepare CrIII acetate typically lead to trinuclear
complexes of the familiar basic carboxylate type (9). Three
3
X X X acetate bridged chromium ions share one central oxide ion,
X Cr Cr X and the remaining sixth coordination site of every chromium
X XX X is occupied by water or other ligands. A large variety of these
(8) complexes, differing in the associated ligands, the nature of the
carboxylate, the counterion, and even the oxidation state, have
been prepared and their physical properties studied. Especially
4.4.2 Oxygen and Sulfur Ligands their magnetic exchange interactions have been the subject of
much controversy.
The violet hexaaquo ion [Cr(OH2 )6 ]3+ is a regular
octahedron with CrO distances in the range 191.5 199.1 pm,
+
depending on the particular compound used for the structure L
determination. EXAFS measurements on dilute solutions have O Cr O
provided information about the second hydration shell; it O O O
appears to contain an average of 13.5 water molecules at a Cr Cr
CrO distance of 402(2) pm.28 L L
O O
The CrIII (aq) ion occurs, for example, in [Cr(OH2 )6 ]Cl3
and in the chrome alums, MCr(SO4 )12H2 O. There are several
stable isomers of the chloride; among these the dark green (9)
trans-[CrCl2 (OH2 )4 ]Cl2H2 O is the commercially available
salt.
The rate of exchange of water with [Cr(OH2 )6 ]3+ is Oxalate (ox, C2 O4 2 ) complexes of CrIII have been
extremely slow (k = 4.5 107 s1 at ambient temperature). known since the very beginning of coordination chemistry.
Extensive mechanistic and kinetic studies suggest that this Thus, the resolution of chiral [Cr(ox)3 ]3 with strychninium
reaction proceeds by an Ia mechanism, that is, associative counterion by Werner in 1912 produced the first optically
interchange. The aquo ion is fairly acidic (equation 7) and active anionic coordination compound. There also exists a
the resulting hydroxo complex dimerizes to the doubly series of bis(oxalato) complexes of the type [Cr(ox)2 X2 ]2+/0 ,
bridged [(H2 O)4 Cr(-OH)2 Cr(OH2 )4 ]4+ , a weakly coupled where X can be any of a variety of neutral donors (e.g. H2 O,
antiferromagnet. Addition of base sets off a stepwise NH3 , etc.) or anionic ligands (e.g. SCN , N3 , etc.). These
polymerization yielding various hydroxy complexes of higher compounds have been used to study the mechanism of cis/trans
nuclearity; some of these have been isolated by ion-exchange isomerization and racemization of optically active octahedral
chromatography. coordination compounds.
Several dioxygen complexes of chromium featuring
H+
superoxide (O2 ) bound to CrIII can be made by
[Cr(OH2 )6 ]3+ [Cr(OH2 )5 (OH)]2+ pKa = 4 exposure of CrII precursors to O2 .31 The first structurally
+H+
characterized example of such an adduct that is,
[(H2 O)4 Cr(-OH)2 Cr(OH2 )4 ]4+ (7) [TptBu.Me Cr(pz H)(O2 )]+ interestingly features the rare
side-on bonding mode of the superoxide ligand.32
Refluxing of CrCl3 (THF)3 in anhydrous alcohols Other oxygen-based donor molecules that form CrIII
yielded purple insoluble solids, which were formulated as complexes include THF (e.g. the synthetically useful
[Cr(ROH)n Cl3 ] adducts (R = Me, Et, i-Pr, n-Bu, n-hexyl). [Cr(THF)3 Cl3 ]), urea ([Cr{OC(NH2 )2 }6 ]3+ ), sulfoxides (e.g.
Various alkoxides of CrIII have been prepared; they have been [Cr(DMSO)6 ]X3 ), amides (e.g. [Cr(DMF)6 ]X3 ), N-oxides,
reviewed in detail.29 Extreme steric congestion is likely to be and phosphine oxides.
responsible for the distorted tetrahedral coordination geometry Introduction of sulfur ligands into the coordination
exhibited by Li[Cr{OCH(t-Bu)2 }4 ]THF.30 sphere of aqueous CrIII has been accomplished by oxi-
Many acetylacetonate complexes and related -diketonates dation of CrII (aq) with various sulfur-containing oxidants.
of CrIII have been made over the years. Many of these are rather There resulted a series of complexes of the composition
volatile, a property that has been exploited for the separation [Cr(SR)(H2 O)5 ]2+ (R = H, alkyl, aryl). They all ultimately
10 CHROMIUM: INORGANIC & COORDINATION CHEMISTRY
suffer substitution of the sulfur ligand by water, that is, aqua- containing pyridine and its derivatives, imidazoles, pyrazines,
tion. In nonaqueous media, a number of thiolato complexes and pyrazoles. They are all six-coordinate octahedral species.
([Cr(SR)3 ], R = Me, Et, Ph, Bz) and thioether adducts of [Cr(bipy)3 ]3+ , the most oxidized member of an electron
CrIII halides ([CrX3 (L)3 ], X = Cl, Br; L = THT, SMe2 , SEt2 ) transfer series extending to [Cr(bipy)3 ]3 , is an example
have been prepared and characterized. There are also many with a chelating ligand. A detailed study of its crystal
complexes containing bidentate sulfur ligands such as dithio- structure and spectroscopic properties has been carried out.36
carbamates, 1,3-dithiodiketonates, 1,2-dithiolates, and so on. Porphyrin ligands fall in this category also, and while
they support chromium in the oxidation states +II to +V,
CrIII porphyrins are the most common ones. For example,
4.4.3 Nitrogen and Phosphorus Ligands [(TPP)CrCl] is soluble in toluene only in the presence
of donor molecules, giving the expected six-coordinate
CrIII complexes of ammonia and amines (both mono- and [(TPP)Cr(L)Cl]. Remarkably, the sixth ligand is fairly labile
polydentate) exist in overwhelming numbers. Representatives and is substituted rapidly, in contrast to the typically slow
of this class of compounds were among the first coordination ligand-substitution reactions of other CrIII complexes. Finally,
compounds to be studied by Werner and his contemporaries. reports on poly(pyrazolyl)borate complexes of CrIII are still
The early work (prior to 1970) on amine complexes relatively rare, despite the recent surge of interest in these
has been reviewed comprehensively.33 Typical complexes
ligands.24
include [CrA6 ]3+ (A = NH3 , amine) and a wide variety of
Amide complexes of trivalent chromium constitute some
mixed ligand systems of the type [CrA6(n+m) Ln Xm ](3m)+
of the rare exceptions from octahedral coordination. Largely
(L = neutral donor ligand, e.g. H2 O; X = monoanionic
because of steric constraints, there are examples of three-
ligand, e.g. halide). Molecular orbital studies confirm that the
and four-coordinate complexes. Both [Cr{N(i-Pr)2 }3 ] and
[Cr(NH3 )6 ]3+ ion does not feature -bonding with the NH3
[Cr(N{SiMe3 )2 }3 ] (12) are monomeric in solution and in the
ligands. Because of the kinetic inertness of CrIII complexes,
solid state and have effective magnetic moments consistent
isomers of various kinds are commonly observed and can
with three unpaired electrons (eff = 3.8 B ). Their crystal
be isolated and characterized. In neutral or basic media,
structures feature trigonal planar CrN3 moieties as well
mixed ammine/aquo complexes form dimers and polynuclear
as planar CrNR2 units. The latter observation, in concert
species with oxo and hydroxo bridges. The simplest of
with short CrN bonds, suggests strong ligand-to-metal -
these are the blue basic rhodo ion (10) and the red
donation. Sterically less demanding amides (NMe2 , NEt2 )
acid rhodo complex (11). Complexes with two or three
lead to dimerization via bridging amido groups and thus
bridging ligands (e.g. -hydroxides) are also very common.
tetrahedral coordination of CrIII . The dimers disproportionate,
The CrIII ions in these complexes are invariably coupled
thereby providing access to CrIV amides [Cr(NR2 )4 ]. A
antiferromagnetically. Much effort has been expended in
four-coordinate CrIII complex with the unusual trigonal
trying to correlate the exchange constant J with structural
monopyramidal geometry is formed by a chelating tris-amido
parameters.34 While it is generally accepted that the coupling
ligand.37
in edge-bridged bioctahedra (two bridging ligands) is mediated
by the bridging ligands, a direct correlation between J and the
metal metal distance of face-sharing d3 d3 systems (three
Me3Si SiMe3
bridging ligands) has also been proposed.35 N
Me3Si Cr SiMe3
N N
4+
H3N NH3 H3N NH3
SiMe3 SiMe3
H3N Cr O Cr NH3 (12)
180 pm
H3N NH3 H3N NH3
(10)
The unusual solid phase Ca3 [CrN3 ] contains sheets of
H3N NH3 H H3N NH3
5+ trigonal planar [CrN3 ]6 units with short CrN bonds (CrN,
O Cr 186.4, 176.6 pm). The effective magnetic moment of 1.86 B
H3N Cr 165.6o NH3 implies a low-spin configuration, unprecedented for a CrIII
HN NH H
3 3 N NH
3 3 complex.38
(11) The hard CrIII ion does not favor soft ligands such as
phosphines and arsines. Nevertheless, phosphine adducts
of the trihalides have been prepared, for example by
Nitrogen heterocycles also form an extensive series of displacement of THF from CrCl3 (THF)3 . Long CrP distances
CrIII complexes, adding a -bonding contribution to the in crystallographically characterized molecules (ca. 247 pm)
metal ligand bond. Complexes of this type include those underscore the weakness of the bonds.
CHROMIUM: INORGANIC & COORDINATION CHEMISTRY 11
Inorganic Chemistry, ed. K. D. Karlin, John Wiley & Sons, 35. A. Niemann, U. Bossek, K. Wieghardt, C. Butzlaff, A. X. Traut-
New York, 2003, Vol. 51, p. 145. wein, and B. Nuber, Angew. Chem., Int. Ed. Engl., 1992, 31, 311.
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13. Gmelins Handbuch der Anorganischen Chemie, Chrom, J. Ferguson, Inorg. Chem., 1987, 26, 1331.
Teil B, Verlag Chemie, Weinheim, 1962. 37. C. C. Cummins, J. Lee, R. R. Schrock, and W. M. Davis,
Angew. Chem., 1992, 104, 1510; Angew. Chem., Int. Ed. Engl.,
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T. Lundstrom, J. Cryst. Growth, 1996, 166, 429.
38. D. A. Vennos, M. E. Badding, and F. J. DiSalvo, Inorg. Chem.,
15. M. R. Pressprich, R. D. Willet, R. D. Poshusta, S. C. Saunders,
1990, 29, 4059.
H. B. Davis, and G. L. Gard, Inorg. Chem., 1988, 27, 260.
39. K. Qin, C. D. Incarvito, A. L. Rheingold, and K. H. Theopold,
16. E. Jacob and E. Willner, Chem. Ber., 1990, 123, 1319.
J. Am. Chem. Soc., 2002, 124, 14008.
17. T. V. Russo, R. L. Martin, and J. P. Hay, J. Chem. Phys., 1995,
40. M. Mitewa and P. R. Bontchev, Coord. Chem. Rev., 1985, 61,
102, 8023.
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Chem. Scand., 1988, A42, 318.
42. J. M. Garrison and T. C. Bruice, J. Am. Chem. Soc., 1989, 111,
19. J. S. Ogden and R. S. Wyatt, J. Chem. Soc., Dalton Trans., 191.
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43. E. G. Samsel, K. Srinivasan, and J. K. Kochi, J. Am. Chem.
20. B. B. Ebbinghaus, Combust. Flame, 1995, 101, 311. Soc., 1985, 107, 7607; K. Srinivasan and J. K. Kochi, Inorg.
21. M. Cieslak-Golonka, Coord. Chem. Rev., 1991, 109, 223. Chem., 1985, 24, 4671.
22. P. A. Lay, A. Levina, in Comprehensive Coordination 44. C. J. Marsden, K. Hedberg, M. M. Ludwig, and G. L. Gard,
Chemistry II, eds. J. A. McCleverty & T. J. Meyer, Elsevier, Inorg. Chem., 1991, 30, 4761.
2004, Vol. 4, p. 313. 45. A. A. Danopoulos, W.-H. Leung, G. Wilkinson, B. Hussain-
23. J. J. H. Edema, S. Gambarotta, F. van Bolhuis, W. J. J. Smeets, Bates, and M. B. Hursthouse, Polyhedron, 1990, 9, 2625.
and A. L. Spek, Inorg. Chem., 1989, 28, 1407. 46. F. A. Cotton and R. A. Walton, Multiple Bonds between Metal
24. S. Trofimenko, Scorpionates, Imperial College Press, London, Atoms, 2nd edn., Oxford University Press, Oxford, 1993,
1999. chap. 4.
25. D. M. Halepoto, D. G. L. Holt, L. F. Larkworthy, G. J. Leigh, 47. F. A. Cotton, E. A. Hillard, C. A. Murillo, and H.-C. Zhou, J.
D. C. Povey, and G. W. Smith, J. Chem. Soc., Chem. Commun., Am. Chem. Soc., 2000, 122, 416.
1989, 1322. 48. J. Losada, S. Alvarez, J. J. Novoa, F. Mota, R. Hoffmann, and
26. G. Irwin and A. D. Kirk, Coord. Chem. Rev, 2001, 211, 25. J. Silvestre, J. Am. Chem. Soc., 1990, 112, 8998.
27. A. Filippou, S. Schneider, and G. Schnakenburg, Angew. 49. M. C. Manning and W. C. Trogler, J. Am. Chem. Soc., 1983,
105, 5311.
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28. A. Munoz-Paez and E. S. Marcos, J. Am. Chem. Soc., 1992,
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1991, 11, 195; F. A. Cotton, J. Czuchajowska, and X. Feng,
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Alkoxides, Academic Press, London, 1978.
52. J. J. H. Edema, S. Gambarotta, P. van der Sluis, W. J. J. Smeets,
30. M. Bochmann, G. Wilkinson, G. B. Young, M. B. Hursthouse,
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31. M. H. Dickmann and M. T. Pope, Chem. Rev., 1994, 94, 569. Acknowledgment
32. K. Qin, C. D. Incarvito, A. L. Rheingold, and K. H. Theopold,
Our investigation of chromium compounds has been supported
Angew. Chem., Int. Ed. Engl., 2002, 41, 2333.
for many years by the U.S. National Science Foundation, as
33. C. S. Garner and D. A. House, Transition Met. Chem., 1970, 6, well as by the Chevron Chemical Co. and its successor, the
59. Chevron Phillips Chemical Co. We thank these organizations
34. C. J. Cairns and D. H. Busch, Coord. Chem. Rev., 1986, 69, 1. for their support.
Chromium: subsequent report from Fischers laboratory describing trans-
halogeno(phenylcarbyne)tetracarbonylchromium.13
Organometallic Chemistry Finally, the history of the chromium carbon bond would
not be complete without mention of the first homoleptic
tetraalkyl, Cr(CH2 SiMe3 )4 , prepared by Wilkinson and
Klaus H. Theopold & Robin R. Kucharczyk his colleagues in 1970.14 By this time, organochromium
University of Delaware, Newark, DE, USA chemistry had become firmly established in the landscape
of organometallic chemistry, and since then a vast array
of molecules in oxidation states ranging from IV
to +VI has been reported in the chemical literature.
1 Introduction 1 Today, organochromium chemistry remains an area of
2 Highly Reduced Chromium Organometallics 1 vigorous research, as chemists seek more stereoselective
3 Chromium(0) Organometallics 2 (arene)chromium reagents, more efficient polymerization
4 Chromium(I) Organometallics 4 catalysts, and novel molecules in unusual oxidation states.
5 Chromium(II) Organometallics 6 This article summarizes the relevant chemistry, with emphasis
6 Chromium(III) Organometallics 10 on recent developments of interest. It is organized by
7 Chromium(IV) Organometallics 13 the increasing formal oxidation state of the metal. Di-
8 Chromium(V) Organometallics 15 and polynuclear compounds are not explicitly covered
9 Chromium(VI) Organometallics 15 here, but can be found in Dinuclear Organometallic
10 Related Articles 15 Cluster Complexes and Polynuclear Organometallic Cluster
11 References 16 Complexes. A book devoted solely to the organometallic
chemistry of chromium was published in 1975.15 More
recent comprehensive reviews are available,16,17 and synthetic
procedures have been summarized very recently.18,19
1 INTRODUCTION
2 HIGHLY REDUCED CHROMIUM
The organometallic chemistry of chromium originated with ORGANOMETALLICS
a pair of early discoveries implying the intermediacy of
organochromium compounds. In 1866, Berthelot1 found that The most familiar compounds containing chromium in
acetylene was reduced to ethylene by salts of chromium(II). negative oxidation states are the binary carbonyl anions, also
Forty eight years later, in 1914 Bennett and Turner2 reported called carbonylmetallates.20 [Cr(CO)5 ]2 has been known for
the coupling of aryl groups derived from Grignard Reagents some time, having been first prepared via alkali metal reduc-
in the presence of chromium(III). It was not until 1957, tion of Cr(CO)6 in liquid ammonia.21 Refinements of this
however, that Anet and Leblanc3 prepared the first pure basic methodology22,23 have allowed for quantitative synthe-
-bonded organochromium compound, [PhCH2 Cr(H2 O)5 ]2+ , sis. The monomeric binary carbonyl anion [Cr(CO)5 ] can be
and Herwig and Zeiss4 synthesized Ph3 Cr(THF)3 . generated electrochemically; its lifetime, however, is only a
Organochromium species containing -bonded ligands few seconds.24 A remarkable superreduced carbonylmetal-
were first prepared by Hein as early as 1919, but were late, [Cr(CO)4 ]4 , is obtained cleanly and in high yield from
not definitively characterized for another 35 years. Hein5 the reduction of the (tetracarbonyl)chromium(0) complex of
reported on the reaction of PhMgBr with CrCl3 to give tetramethylethylenediamine (equation 1).25 The success of
Chromorganoverbindungen; this synthesis was reproduced this reaction is attributed to reductive labilization, whereby
by Zeiss and Tsutsui6 in 1954, at which time they preferential loss of the poorest acceptor ligand occurs upon
identified the products as bis(arene)chromium cations. Shortly reduction.
thereafter, Fischer and Hafner7 published their route to neutral NH3 (l)
bis(benzene)chromium. This early work has been chronicled, (TMEDA)Cr(CO)4 + 4Na Na4 (Cr(CO)4 + TMEDA (1)
most recently by Seyferth.8
The diverse chemistry of chromium carbonyl complexes [Cr(CO)5 ]2 is a light yellow, extremely air-sensitive
has its origin in the discovery of Cr(CO)6 in 1926 powder. Back Bonding to the carbonyls is extensive here,
by Job and Cassal.9 Early developments in this area and is reflected in the median value of vCO , 1750 cm1 .23 This
included the preparation of the (6 -arene)Cr(CO)3 family dianion is a strong base, a good nucleophile, and a powerful
of organometallics by Nicholls and Whiting in 1959,10 reducing agent (equations 2 4).23,26,27
the synthesis of the first structurally characterized carbene
complex by Fischer and Maasbol (1965),11,12 and a 2[Cr(CO)5 ]2 + 3H2 O [HCr2 (CO)10 ] + H2 + 3OH (2)
2 CHROMIUM: ORGANOMETALLIC CHEMISTRY
[Cr(CO)5 ]2 + CN + 2H2 O [Cr(CO)5 CN] + 2OH + H2 (3) shows a single sharp band at 1984 cm1 .
[Cr(CO)5 ]2 + Cl2 CS 2Cl + Cr(CO)5 (CS) (4)
Et2 O
CrCl3 + xsCO + LiAlH4 Cr(CO)6 (5)
Yellow pyrophoric [Cr(CO)4 ]4 gives an IR spectrum h
consistent with its structure and with a Formal Oxidation Cr(CO)6 Cr(CO)5 + CO (6)
State of 4: the most intense carbonyl band appears at
1462 cm1 . Reaction with three equivalents of Ph3 SnCl in two Chromium hexacarbonyl is extremely photolabile (equa-
steps yields [(Ph3 Sn)3 Cr(CO)4 ] , the first seven-coordinate tion 6); therefore photochemical substitution is an efficient
chromium compound with exclusively monodentate ligands. means of preparing derivatives.33 Oxidation of the Cr0 cen-
More efficient is the synthesis of [(Ph3 Sn)2 Cr(CO)4 ]2 from ter requires nitric or sulfuric acid, or chlorine. Alternatively,
(TMEDA)Cr(CO)4 and Ph3 SnLi, followed by addition of some ligands induce complete carbonyl dissociation with con-
Ph3 SnCl. These moderately air-sensitive organometallics comitant oxidation, for example, acetylacetonate. Chemical
can be isolated as their Et4 N+ salts. A single-crystal X- reduction with alkali or alkaline-earth metals or electrochem-
ray study of the tris(triphenyltin) anion confirmed the ical reduction proceeds in two-electron steps with loss of
presence of heptacoordinate chromium.28 The tetraanion also two CO molecules to first give [Cr2 (CO)10 ]2 and then
reacts with NH4 Cl to give Cr(CO)4 (NH3 )2 (rather than the [Cr(CO)5 ]2 . Nucleophilic attack at CO generates a number of
anticipated [H3 Cr(CO)4 ] ), and with excess MeCN to give stable (Nu = R) and unstable (Nu = N3 , OH, H, NEt2 ) prod-
[H2 Cr(CO)8 ]2 . Further information on the reactivity of these ucts. The stable [(OC)5 CrCOR] ion is a carbene precursor.
carbonylmetallates and their derivatives can be found in a
review article describing these compounds.29
3.2 Substituted Chromium(0) Carbonyls Without
Substituted compounds of chromium in negative oxida-
Carbon Ligands34
tion states are also known. Two apparent examples are
[(6 -C6 H6 )Cr(CO)3 ]2 and [(bipy)Cr(CO)4 ] .30,31 An EPR The derivatives of chromium hexacarbonyl, Cr(CO)6x
spectrum of the latter compound, however, indicated that (L)x , make up the single largest class of organochromium
the unpaired electron resides within the aromatic ring; this compounds, and a substantial number of these are Cr0
result implies that chromium is actually in the zero oxida- compounds as well. The most common synthetic route
tion state, bound to (bipy) .23 Finally, potassium reduction of involves direct reaction of Cr(CO)6 and x L, but displacement
Cr(6 -C6 H6 )2 yielded the corresponding radical anion [Cr(6 - of a weakly bound ligand from a carbonyl derivative is
C6 H6 )2 ] , a Cr(-I) compound without any carbonyl ligands, also frequently employed. Carbonyl dissociation is usually
which was characterized by ESR spectroscopy.32 promoted with heating or UV irradiation.
The rare chromium carbonyl fluoride [Cr(CO)5 F] can
be prepared oxidatively or by substitution; it is stable in air
for short periods. Protonation of [Cr(CO)5 ]2 with methanol
3 CHROMIUM(0) ORGANOMETALLICS yields the carbonyl hydride [HCr(CO)5 ] ,35 isolable as the
Et4 N+ or Ph4 As+ salt. Its hydride resonance in the 1 H NMR
spectrum is located at 7.0 ppm. Since -donor nitrogen
This section highlights some of the significant features of ligands lack the acceptor ability of CO, an ability that
chromium(0) carbonyls and of the chemistry of this oxidation minimizes the buildup of electron density on chromium
state. Further information can be found in the articles Carbonyl trisubstitution is the maximum extent of reaction observed,
Complexes of the Transition Metals and Organic Synthesis for example, between Cr(CO)6 and NH3 . Nucleophilic attack
using Transition Metal Carbonyl Complexes, and in the of an azide at a carbonyl carbon of Cr(CO)6 gives an
review literature.15,16 isocyanate following a Curtius-type degradation (Scheme 1).
(Ammine)pentacarbonylchromium undergoes a condensation
3.1 Chromium Hexacarbonyl reaction with acetone in the presence of a drying agent to give
the (ketimine)pentacarbonyl compound.
This colorless, volatile, and air-stable solid is the starting
material for synthesis of many Cr0 derivatives. Commercially
O
available, it is seldom synthesized; however, Reductive N2
N3
Carbonylation (e.g. equation 5) gives higher yields and is Cr(CO)6 (OC)5Cr [(OC)5Cr(NCO)]
fast
more reliable than other methods. Cr(CO)6 melts at 130 C, slow N
sublimes at room temperature in vacuo, and dissolves slightly N2
in organic solvents. It exhibits perfect octahedral symmetry,
as determined by electron and neutron diffraction and X-ray
crystallography. The IR spectrum of this material in CCl4 Scheme 1
CHROMIUM: ORGANOMETALLIC CHEMISTRY 3
Cr(CO)5 (THF), an O-donor derivative, is synthetically use- been prepared using the novel reagent N3 S3 Cl3 with [(5 -
ful as a source of the unsaturated fragment Cr(CO)5 , as the C5 H5 )Cr(CO)3 ] .43 On the basis of CO stretching frequencies,
weakly bound cyclic ether is easily dissociated or displaced.36 it is likely that NS is even superior to NO as a -acceptor.
By contrast, phosphines (PR3 ), phosphites (P(OR)3 ), phospho- Other Cr0 complexes containing sulfur, as well as selenium
rus halides (PX3 ), phosphorus amines (P(NR2 )3 ), phosphinites and tellurium ligands, have been described.16,17
(PR2 (OR)), and phosphonites (PR(OR)2 ) are -donor/ -
acceptor ligands that readily substitute for THF, forming stable
derivatives. The better -acceptors, P(OR)3 and PF3 , can form 3.3 Substituted Chromium(0) Carbonyls with -donor
the homoleptic compounds Cr{P(OR)3 }6 and Cr(PF3 )6 . A vast Carbon Ligands
number of Cr0 complexes containing carbonyl and phosphorus
ligands can be found in the literature;37,38 the reader is referred Among the types of complexes found here are formyl,
to these sources for information on specific complexes, syn- acyl, alkyl, and aryl carbonyls, carbonyl cyanides,44 carbonyl
theses, and reactions. Forcing conditions are necessary to isocyanides and acetylides,45 and thiocarbonyl and seleno-
form carbonyl compounds of the remaining group 15 lig- carbonyl complexes.46 Of the greatest significance, however,
ands. As with the phosphorus derivatives, polydentate ligands are the chromium carbenes, for example, (CO)5 Cr=C(OR)R .
and unusual compounds have been reported, for example, This chemistry has been thoroughly reviewed;47 nevertheless,
Scheme 2. An X-ray crystallographic structure revealed very these compounds will be briefly discussed here.
short As=Cr bonds in this molecule, that is, 2.38 A. The first carbene compound to be well characterized
The nitrosonium ion39 and the alkyl- and aryldiazonium was prepared in 1966 and was one of many Fischer-Type
ions40 are -acceptor ligands that are isoelectronic with
Carbene Complexes to be reported (see equation 7). Fischer
carbon monoxide. Other -acceptors are characterized
carbenes are characterized by heteroatom substituents at the
by the -diimine moiety; these include the stabilizing
carbene carbon, stabilization by a low-valent metal center,
ligands bipy, phen, and terpy. Mononitrosyl complexes of
and a partial positive charge at the carbene carbon. In
chromium(0) have been known for some time (Scheme 3);41
contrast, Schrock-Type Carbene Complexes, or alkylidenes,48
recently renewed interest in (nitrosyl)chromium species has
that have alkyl substituents, are found on metal centers in
led to the development of routes to (5 -C5 H5 )Cr(NO)2 X
higher oxidation states, and are nucleophilic at carbon. Many
(X = CH2 SiMe3 , Cl, Me, FPF5 ) and [(5 -C5 H5 )Cr(NO)2 L]+
Fischer carbenes are known for chromium, whereas chromium
(L = PPh3 , NCR, CNR, py, H2 NAr). A recent review of
alkylidenes are much less common. Monohalocarbenes of
organometallic metal-NO complexes, including chromium
chromium, for example, (OC)5 Cr=C(F)NEt2 , have also been
compounds, is available.42 The first thionitrosyl complex has
extensively investigated.49 Two carbene reactions of note for
their application to organic synthesis are the cycloaddition of
[(OC)5CrAsPh]2 (OC)5Cr Ph
alkenes with carbene complexes and the reaction of aromatic
carbenes with alkynes to yield complexed naphthols (the Dotz
+ As As
Ph Cr(CO)5 reaction).50
(OC)5Cr(AsPhCl2)
PhLi MeI
Scheme 2 Cr(CO)6 [(OC)5 C=C(O)Ph] (OC)5 Cr=C(OMe)Ph (7)
Cr(CO)3
NOCl
trans-Cr(CO)2(PEt3)2(NO)Cl 30 C, THF (h5-C5H5)Cr(CO)2(NO)
PEt3 C5H5Na
Cr(CO)2(NO)Cl
mer-Cr(L)3(CO)(NO)Cl cis-Cr(CO)2(NO)(L)Cl
Scheme 3
4 CHROMIUM: ORGANOMETALLIC CHEMISTRY
group by the incoming bidentate ligand. Finally, cleavage That the chemistry of [(5 -C5 H5 )Cr(CO)3 ]2 reflects the
of a nitrosyl iodide dimer, [(5 -C5 H5 )Cr(NO)I]2 , with reactivity of the monomer can be seen in the products of atom
AgPF6 in MeCN affords the nitrosylbis(acetonitrile) cation. abstraction, ligand substitution, and disproportionation reac-
These four compounds exhibit a range of stabilities. tions. A number of phosphine derivatives have been prepared;
[(5 -C5 H5 )Cr(NO)2 L2 ] PF6 is extremely robust, while the however, only (5 -C5 H5 )Cr(CO)2 PPh3 was sufficiently robust
bis(acetonitrile) cation and the chloronitrosyl complex can to be isolated in a crystalline form and fully characterized.
be handled briefly in air as solids. Magnetic moments In addition, dppm, dppe, and dppb gave stable dispropor-
are appropriate for d5 low-spin systems: 1.47 1.96 B tionation products. A comparative study of the analogous
(spin-only value = 1.73 B ). Structure determinations (5 -C5 Me5 ) dimer and monomer revealed a longer, weaker
carried out on (5 -C5 H5 )Cr(NO)(PPh3 )CH2 SiMe3 and CrCr bond than is present in the cyclopentadienyl dimer;62
on [(5 -C5 H5 )Cr(NO)(NCCH3 )2 ]PF6 revealed a three- reactivity toward t-BuNC and smaller phosphines (e.g. PMe3
legged Piano Stool Structure for both with no and P(OMe)3 ), yielding very air sensitive, thermally labile
geometric distortions attributable to the effects of
derivatives, and participation in atom abstraction reactions to
the unpaired electron in these metallaradicals. Studies
form labile halo, hydrido, alkyl, and tributyltin compounds of
of the reactivity of the trimethylsilylmethyl cation
(5 -C5 Me5 )Cr(CO)3 . Crystal-structure determinations have
provided routes to two novel compounds. Treatment
been carried out on (5 -C5 Me5 )Cr(CO)2 PPh3 and on (5 -
with NO, NO+ , and 2HSnPh3 led to isolation of (5 -
C5 Me5 )Cr(CO)2 PMe3 . Both exhibit monomeric three-legged
C5 H5 )Cr(NO)2 CH2 SiMe3 , [(5 -C5 H5 )Cr(NO)2 (PPh3 )]PF6 ,
piano-stool structures. The unusually small OCCrCO bond
and (5 -C5 H5 )Cr(NO)(PPh3 )(SnPh3 )H (see Section 5.2).
Among the 17-electron species are those in which the angles, 80.9 C and 79.9 C, respectively, contrast with the
Cyclopentadienyl ligand and a cyclic triene or arene form approximate value of 90 C for similar Eighteen Electron
an unsymmetrical sandwich complex. The most familiar Compounds and are believed to represent a deformation asso-
example, (5 -C5 H5 )Cr(6 -C6 H6 ),57 is synthesized from CrCl3 , ciated with location of the electron hole between the carbonyl
either C5 H5 MgBr or NaC5 H5 , and PhMgBr. Very reactive, it ligands.
does not undergo Friedel Crafts acylation but rather a ring
expansion (Scheme 5), yielding [(5 -C5 H5 )Cr(7 -C7 H6 R)]+ .
In the presence of cycloheptatriene and AlCl3 or azulene and 4.3 Arene, Bis(Arene), and Other -ligand Compounds
BF3 Me2 O, arene replacement occurs to give [5 -C5 H5 )Cr(7 - of Chromium(I)
C7 H7 )]+ and [(5 -C5 H5 )Cr(7 -azulenium)]+ , respectively.
Its permethylated analogue, (5 -C5 Me5 )Cr(6 -C6 Me6 ), has Monoarene complexes of the form [(6 -C6 R6 )Cr(CO)2 L]+
been obtained from the thermal reaction of dimeric [(5 - (R = H, Me; L = CO, PR3 ) may be prepared from the
C5 Me5 )Cr(-Cl)Me]2 and excess 2-butyne.58 Photolysis corresponding 18-electron species via chemical or elec-
of a mixture of (5 -C5 H5 )CrCl2 THF, i-PrMgBr, and trochemical oxidation. The (benzene)tricarbonyl chromium
cycloheptatriene yields the (6 -C7 H8 ) sandwich; air oxidation cation is of limited stability; however, substituted arene
converts this to the cationic cycloheptatrienyl complex. complexes, for example, [(hexaethylbenzene)Cr(CO)3 ]+ ,
Substitution of 1,3,5-cyclooctatriene or cyclooctatetraene in exhibit appreciable lifetimes on the cyclic voltam-
this preparation gives the analogous (6 -C8 H10 ) and (6 - metric timescale.63 Substantially more robust are the
C8 H8 ) products. The latter can be protonated and reacted dicarbonyl cations [(6 -C6 Me6 )Cr(CO)2 L]+ (L = PPh3 ,
with R (R = H, Me), forming (5 -C5 H5 )Cr(7-R-1,3,5- PMePh2 , PMe2 Ph), [(6 -biphenyl)Cr(CO)2 PPh3 ]+ , and [(6 -
cyclooctatriene). C6 Me6 )Cr(CO)2 (RCCR)]+ (R = Ph, 4-MeOC6 H4 ).
Recent interest in metal-centered radicals59,60 has prompted Unlike bis(benzene)chromium itself, the bis(benzene)chro-
numerous studies of the 17-electron monomers (5 - mium cation and its numerous substituted analogues are air sta-
C5 H5 )Cr(CO)3 and (5 -C5 Me5 )Cr(CO)3 , present to various ble as solids and in solution. Three of these compounds, [(6 -
extents at ambient temperature via dissociation of the parent benzene)2 Cr]+ , [(6 -benzene)(6 -biphenyl)Cr]+ , and [(6 -
dimers (e. g. equation 10).61 biphenyl)2 Cr]+ , were isolated by Hein during his historic
work with Chromorganoverbindungen in 1919.5 Crystal
[(5 -C5 H5 )Cr(CO)3 ]2
2(5 -C5 H5 Cr(CO)3 ) (10)
structures feature eclipsed arene rings, and magnetic moments
lie within the range 1.70 1.80 B .15 These cations are derived
PF6 from oxidation of (6 -arene)2 Cr. Alkyl and aryl halides, RX,
R
1. RCOCl, AlBr3 oxidize bis(arene) complexes with the formation of R, which
Cr Cr subsequently abstracts hydrogen, disproportionates, or dimer-
2. H2O, NH4PF6
izes. Halogen oxidation is also effective in some cases. Most
reactions of [(6 -arene)2 Cr]+ are reductive in nature or decom-
pose the molecule. Acid-promoted and oxidative routes to the
Scheme 5 free arene are also known.
6 CHROMIUM: ORGANOMETALLIC CHEMISTRY
5 CHROMIUM(II) ORGANOMETALLICS
Me Me
Me Cr Me
[Li(OEt2)]4
5.1 Mono-, Di-, and Poly(organo)chromium(II)
Me Cr Me
Compounds CrCl2(THF)2
Me Me
Significantly fewer complexes of these types are known
for chromium(II) than for chromium(III). Solvated species Et2O 4MeLi,
Et2O TMEDA
are of the general formula Rn CrCl2n Sx and can be TMEDA
prepared directly from CrX2 or CrX2 (THF)2 (X = Cl, Br)
and one or two equivalents of Grignard reagents. Only
two mono(organo) compounds, (1-naphthyl)CrBr(THF) and Me Me
N N
its 1-(2-methyl)naphthyl analog, have been prepared in Li Cr Li
this manner. The only other RCrClSx complex, a mesityl N Me Me N
chloride, was obtained via ligand exchange between solvated
bis(mesityl)chromium and CrCl2 .
In contrast, numerous examples of R2 CrSx have Scheme 6
been synthesized by the Grignard route, for
example, (mesityl)2 CrSx (Sx = (THF)3 or (THF)(bipy)), moment of 4.82 B , the spin-only value for a system with
(Ph)2 Cr(bipy)2 , and (o-anisyl)2 Cr(bipy)2 . One finds that four unpaired electrons being 4.9 B . These values can be
substitution of an N- or P-donor ligand for THF in compared with the value of 3.22 B for (Ph)2 Cr(bipy)2 ,
these molecules stabilizes them considerably. For example, which is indicative of a system with only two electrons
(Ph)2 Cr(THF)n is an unstable brown solution at temperatures unpaired (spin-only value = 2.8 B ). Little is known about
of 30 C and above, whereas the bipy solvate is an the chemistry of these organochromium(II) compounds. Most
isolable blue solid. Alternatives to the Grignard route include have been shown to react with HgCl2 to give RHgCl and
reaction with lithium reagents (equation 11) or thermal Hg2 Cl2 , and to undergo the same CrC bond cleavage in
transformations of tri(organo)chromium(III) species and metal the presence of I2 . Hydrolysis and oxidation are two other
poly(organo)chromates (equation 12). reactions reported for some complexes.
2PhLi 2bipy
CrCl2 (THF)2
Ph2 Cr(THF)n Ph2 Cr(bipy)2 (11) 5.2 Chromium(II) Hydrides
70 C
, THF
Ph2 CrII (bipy)2 + Ph2 CH The majority of compounds in this family can be described
Ph2 CrIII (CHPh2 )(THF)n (12)
bipy by the formula (5 -C5 R5 )CrL1 L2 L3 H, where R = H or Me and
L1 L3 represent some combination of three carbonyl and/or
Chromium(II) polyorganochromates, M2 CrR4 , exist as phosphine ligands (see Hydride Complexes of the Transition
monomers and as dimers; the latter are discussed in Dinuclear Metals). The most familiar hydride, (5 -C5 H5 )Cr(CO)3 H, is
Organometallic Cluster Complexes. Reaction of appropriate obtained from the reaction of chromocene with CO and H2 .
lithium reagents with CrBr2 (THF)2 yields the three complexes Addition of cyclopentadiene to (MeCN)3 Cr(CO)3 also affords
Li2 [Cr(N -methylpyrrolyl)4 ](THF)3 , Li2 [CrPh4 ](THF)4 , and the desired product, as does the synthesis from Cr(CO)6
Li2 [Cr(mesityl)4 ](THF)4 . The tetraphenyl compound may and a metal cyclopentadienide followed by protonation. A
also be prepared from PhLi and (Ph)2 CHCr(Ph)2 (THF)n . weak acid, this thermally unstable species readily loses a
Reversible cleavage of the chromium chromium quadruple molecule of hydrogen en route to reversible formation of the
bond of [Cr2 Me8 ][Li(L)]4 (L = THF, Et2 O) gives the high- dimer [(5 -C5 H5 )Cr(CO)3 ]2 . Reactions include carboxylation
spin species Li2 CrMe4 .64 Cleavage is achieved by replacing in the presence of BF3 Me2 O to give [(5 -C5 H5 )Cr(CO)4 ]BF4
the Lewis base coordinated to the lithium with TMEDA. and preparation of compounds containing chromium metal
Alternatively, the compound can be synthesized from bonds. This hydride is also known to be an active catalyst
CrCl2 (THF)2 and four equivalents of MeLi in Et2 O with an for the hydrogenation of conjugated dienes, for example,
excess of TMEDA present (Scheme 6). Analogous complexes isoprene; however, the (6 -arene)Cr(CO)3 system exhibits far
(TMEDA)CrR2 (R = CH2 Ph, CH2 CMe3 , CH2 C(Ph)Me2 ) greater stereoselectivity.
have been prepared as well.65 The (5 -C5 Me5 ) analogue of (5 -C5 H5 )Cr(CO)3 H was first
As a rule, these compounds are very sensitive to oxygen identified in 1983,66 but no details of its preparation or charac-
and water. The solvated compounds tend to lose solvent terization were mentioned. A subsequent report described
molecules in vacuo. Magnetic measurements reveal the several synthetic routes: from [(5 -C5 Me5 )Cr(CO)2 ]2 and
presence of high-spin and low-spin CrII species within moist LiPF6 in CH2 Cl2 or H2 O in toluene, from treat-
this group. (Mesityl)2 Cr(THF)3 has an associated magnetic ment of [(5 -C5 Me5 )Cr(CO)3 ]Na with acetic acid, and from
CHROMIUM: ORGANOMETALLIC CHEMISTRY 7
(MeCN)3 Cr(CO)3 and C5 Me5 H.67 It is also formed in the reac- Interestingly, the isotopomers (5 -C5 Me4 Et)4 Cr4 (-H)x (m-
tion of (5 -C5 Me5 )Cr(CO)3 with H2 S, the other products being D)4x exhibit extremely large isotope effects on the
13
(5 -C5 Me5 )Cr(CO)3 SH and [(5 -C5 Me5 )Cr(CO)2 ]2 (-S).68 C NMR chemical shifts of the cyclopentadienyl ligands
(5 -C5 Me5 )Cr(CO)3 H is a sublimable, air-sensitive crystalline ( = 0.373.06 ppm per H/D substitution). This effect has
solid. Solutions turn dark red when exposed to air or O2 , been used to measure the barrier for the exchange of the
indicative of the presence of an unidentified transient species, hydride ligands (G = 12 kcal mol1 ).71 Further addition
which decomposes in the absence of O2 . at H2 at high pressure produced the hydride cluster (5 -
The hydride (5 -C5 H5 )Cr(P(OMe)3 )3 H has been prepared C5 Me4 Et)4 Cr4 (-H)7 , which was structurally characterized
quantitatively from (5 -C5 H5 )CrCl2 (THF), NaBH4 , and by neutron diffraction. This mixed-valent (CrIII 3 CrII ) molecule
excess P(OMe)3 . Treatment of this product with CO results has a spin state of S = 7/2.72
in a single substitution, and (5 -C5 H5 )Cr(P(OMe)3 )2 (CO)H
forms. Reaction with CCl4 oxidizes the chromium center,
5.3 Carbonyl Compounds of Chromium(II)
giving (5 -C5 H5 )CrCl2 (P(OMe)3 ). Nitrosylation yields one of
two products, monomeric (5 -C5 H5 )Cr(P(OMe)3 )2 NO or the This section describes chromium(II) species with two or
hydride-bridged dimer {(5 -C5 H5 )Cr(NO)2 }2 (2 -H). more carbon monoxide ligands; (cyclopentadienyl)chromium
The substituted hydride (5 -C5 R5 )Cr(CO)2 (CDPP)H (R = carbonyls are presented separately (Section 5.4). An unusual
H, Me; CDPP = cyclohexyldiphenylphosphine) was one of seven-coordinate cation, [Cr(CO)2 (diars)2 X]+ (X = Br, I),
several products formed following substitution of phosphine was prepared via oxidation of the precursor Cr(CO)2 (diars)2
for carbonyl in the 17-electron moiety (5 -C5 R5 )Cr(CO)3 . with X2 . This complex is an 18-electron, diamagnetic halide
This complex could also be synthesized by refluxing salt. An excess of X2 does not oxidize it to CrIII ; instead,
the chromium tricarbonyl dimer and CDPP in ethanol. only the trihalide salt is isolated. [Cr(CO)4 (SnPh3 )3 ] , a
Crystallographic analysis revealed a four-legged piano-stool heptacoordinate anion, is the product of the reaction of
structure with cis carbonyl ligands. cis-[Cr(CO)4 (SnPh3 )2 ]2 with one equivalent of SnPh3 Cl.
The first hydrido nitrosyl compound to be isolated, The first thermally stable chromium carbonyl species with
(5 -C5 H5 )Cr(NO)(PPh3 )(SnPh3 )H, was derived from (5 - seven monodentate ligands, it is subject to loss of a
C5 H5 )Cr(NO)(PPh3 )(CH2 SiMe3 ) and two equivalents of triphenylstannyl group via reduction or bond heterolysis.
HSnPh3 . Its chemistry is yet to be investigated. Electrochemical oxidation of Cr(CO)5 X (X = Cl, Br, I)
Other CrII hydrides of interest include (5 - generated the halopentacarbonyl cations [Cr(CO)5 X]+ at
C8 H11 )Cr(PF3 )3 H and (6 -C6 H6 )Cr(CO)2 (SiCl3 )H. The 75 C. The room-temperature instability of these species,
former complex was obtained in 2% yield upon cocon- as well as the potentials required for their formation, were
densation of chromium vapor, cyclooctadiene, and PF3 ; its shown to account for the inability to produce [Cr(CO)5 X]+
structure was verified crystallographically.69 Although the previously by chemical means. Finally, a bis(trichlorosilyl)
hydridic hydrogen was not located, its 1 H NMR signal was complex, (6 -C6 H6 )Cr(CO)2 (SiCl3 )2 , was obtained from the
observed. Of mechanistic significance is the fact that this photolysis of (6 -C6 H6 )Cr(CO)3 in the presence of excess
molecule is structurally equivalent to an intermediate in the HSiCl3 .
interconversion of (1,3-) and (1,5-cyclooctadiene)Cr(PF3 )3
by the -allylhydrido mechanism (Scheme 7). Preparation 5.4 (5 -cyclopentadienyl)chromium(II) Carbonyl
of the latter involves UV irradiation of a mixture of (6 - Compounds
C6 H6 )Cr(CO)3 and HSiCl3 ; IR spectral evidence indicates
a distorted square-pyramidal structure with an apical arene Chromium compounds of this type feature one to four
ligand and cis carbonyls. carbonyls and one or more ancillary ligands, as seen, for
In this context, the tetranuclear hydride clusters [(5 - example, in (5 -C5 H5 )Cr(CO)2 (3 -allyl). A general synthesis
C5 Me5 )Cr(-H)]4 and [(5 -C5 Me4 Et)Cr(-H)]4 should be for allyl complexes of this type, including the aforementioned
mentioned; they adopt a cubane-type structure and exhibit parent complex has just been published.73 Alternatively,
antiferromagnetic coupling between the CrII centers.70 the reaction of butadiene with [(5 -C5 H5 )Cr(CO)3 ]2 in the
presence of mercury yields the 3 -C4 H7 crotyl derivative in
a photolytic preparation. (5 -C5 H5 )Cr(CO)2 (3 -C5 H7 ) forms
as a by-product of the reaction of (5 -C5 H5 )2 Cr with CO and
H2 to give (5 -C5 H5 )Cr(CO)3 H. The latter two allyls were
Cr
initially formulated as (4 -cyclopentadiene)Cr0 (CO)2 (4 -
Cr Cr
F3P PF3 F3P PF3 F3P PF3 diene) (diene = C4 H6 , C5 H6 ), but their true structures
PF3 H PF3 PF3 were later established by 1 H NMR studies. Photolysis
of solutions containing (5 -C5 H5 )Cr(CO)3 Me and
PR3 (R = Ph, OMe) leads to isolation of (5 -
Scheme 7 C5 H5 )Cr(CO)2 (PPh3 )Me, (5 -C5 H5 )Cr(CO)2 (PPh3 )COMe,
8 CHROMIUM: ORGANOMETALLIC CHEMISTRY
and (5 -C5 H5 )Cr(CO)(P(OMe)3 )2 Me as air-sensitive Chromocene is a volatile and reactive solid with a
crystalline solids. Trimethyl phosphite complexes analogous magnetic moment of 3.27 B . Comparison of this value
to the two obtained with PPh3 can be prepared using with the spin-only value, 2.83 B , suggests the presence
one equivalent of the reagent; these are sufficiently of a significant orbital contribution. An electron diffraction
robust to undergo spectroscopic characterization, but too study favors eclipsed cyclopentadienyl rings in (5 -C5 H5 )2 Cr
unstable to separate and crystallize. The acetyl species (D5d symmetry); however, a staggered configuration (D5h
are thought to form from the attack of a photochemically symmetry) remains plausible, particularly in view of the low-
activated methyl group on a cis-CO ligand. Other barrier-to-ring rotation (<3.8 kJ mol1 ).
(dicarbonyl)phosphine compounds that have been reported The chromocene molecule undergoes reaction with a
include trans-(5 -C5 H5 )Cr(CO)2 (PMe2 Ph)(PCl2 )74 and (5 - wide variety of substrates; these processes have been
C5 H5 )Cr(CO)2 (PR3 )Et (R = OMe, OEt). recently summarized.75 Transformations of note include the
Chromium(II) compounds of the form (5 -C5 H5 )Cr(CO)3 X exchange of cyclopentadienyl rings between (5 -C5 H5 )2 Cr
are numerous. The ligand X may be a halide or alkyl, and Li(C5 D5 ), providing a straightforward synthesis of the
or may be derived from a main-group or transition-series deuterated compound, the reaction with cold deoxygenated
element. Table 1 lists some of these molecules and their HBF4 to form [(5 -C5 H5 )Cr(OH2 )3 ]BF4 , and the elimination
syntheses. As a rule, these seven-coordinate complexes of one aromatic ring with the cleavage of a second in the
exhibit greater thermal instability and air sensitivity than their generation of binuclear [(5 -C5 H5 )Cr]2 (2 ,4 ,4 -C8 H8 ) from
molybdenum and tungsten congeners. Most will decompose chromocene and Na2 C8 H8 .
at ambient temperature, even in an inert atmosphere, While not catalytically active itself, chromocene deposited
and rapidly if exposed to oxygen. The compounds (5 - on silica yields a highly active catalyst, known as the Union
C5 H5 )Cr(CO)3 X (X = (triars)Cu, 1 -CH2 CH=CH2 , CH2 Ph, Carbide catalyst, for the polymerization of ethylene.76 It
CH2 CN, CH2 CO2 Et, or CH(CO2 Me)2 ) were all identified is thought that (5 -C5 H5 )Cr moieties on the silica surface
in solution on the basis of spectral data, but were too constitute the active sites for polyethylene synthesis. This
unstable to be isolated. Similar properties were observed catalysts high hydrogen response allows for the synthesis
for (5 -C5 Me5 )Cr(CO)3 X (X = I, Br, Cl, Me, Bn, 1 -C3 H5 , of polymers having a wide range of molecular weights via
or SnBu3 ). The examples in Table 1, however, are all stable adjustment of the hydrogen-to-ethylene ratio. For a given ratio,
solids, and most are crystalline. however, a relatively narrow molecular weight distribution is
The tetracarbonyl cation [(5 -C5 H5 )Cr(CO)4 ]+ is the obtained. In spite of vigorous research spanning 30 years,7779
product of the reaction of (5 -C5 H5 )Cr(CO)3 H with CO in many other features of this catalytic reaction, for example, the
the presence of BF3 Me2 O. The moisture-sensitive product is mechanism of initiation and the oxidation state of the active
isolated as the tetrafluoroborate salt. chromium species, remain controversial, and so studies of the
chromocene silica system and of potential model compounds
continue.
5.5 Chromocene
X Synthesis Comments
X (X = Br, I) Hg[(5 -C5 H5 )Cr(CO)3 ]2 + X2 Cl2 gives product with no CO ligands
R (R = Me, Et) [(5 -C5 H5 )Cr(CO)3 ] + RI Identity of Et compound questioned
CH2 CO2 Me [(5 -C5 H5 )Cr(CO)3 ]2 + BrCH2 CO2 Me
PCl2 [(5 -C5 H5 )Cr(CO)3 ] + PCl3 Conversion to P(=S)Cl2 compound increases
stability
PO(CMe2 )2 O [(5 -C5 H5 )Cr(CO)3 ] + CIPO(CMe2 )2 O Dioxaphospholane ligand
AsMe2 [(5 -C5 H5 )Cr(CO)3 ] + Me2 AsCl Quite stable; As can be quaternized with MeI
SiH3 [(5 -C5 H5 )Cr(CO)3 ] + H3 SiBr No solvent used; first silyl complex of this type
SnMe3 (5 -C5 H5 )Cr(CO)3 H + Me3 SnNMe2 CO atmosphere
(CH3 CN)3 Cr(CO)3 + (5 -C5 H5 )SnMe3 CO atmosphere
MPh3 (M = Ge, Sn, Pb) [(5 -C5 H5 )Cr(CO)3 ] + Ph3 MCl Stability: Pb<Ge, Sn
AuPPh3 (5 -C5 H5 )Cr(CO)3 H + Ph3 PAuCl Diamagnetic
HgX (X = Cl, Br, I) Hg[(5 -C5 H5 )Cr(CO)3 ]2 + HgX2
CHROMIUM: ORGANOMETALLIC CHEMISTRY 9
this way, compounds with Ln = CO, (NH3 )4 , (NH3 )9 , and enforced rotational orientation of the ligands has been
(2 -F3 CCCCF3 ) have been prepared.75 None of these noted in substituted bis(indenyl)chromium complexes.88
adducts, however, persist at temperatures greater than 20 C. Supported indenyl, fluorenyl, and pentadienyl derivatives
Thermally stable aminates, (5 -C5 H5 )2 Cr(RNH2 )x (R = Et, function as Union Carbide-type catalysts, catalyzing the
Pr, Bu, CH2 =CHCH2 ; x = 4.55.5), form at 25 C upon polymerization of ethylene. Oxidation of the air-stable
exposure of chromocene to the vapors of primary linear bis(metallocarborane)chromium by chemical or electrochem-
amines; like the carbonylation and ammoniations just men- ical means yields the stable CrIII anion. Bis(pentadienyl)
tioned, this reaction is reversible. The first irreversible adduct compounds undergo naked metal reactions analogous to
formation was observed with an N-heterocyclic carbene, those of Ni(allyl)2 , yielding homoleptic bisphosphines and
to give (5 -C5 H5 )Cr(1 -C(NAr)2 C2 H2 )(1 -C5 H5 ).80 Other isocyanides. By contrast, the half-open chromocenes, whose
examples of thermally stable, irreversibly formed deriva- pentadienyl ligands adopt the 5 -S (sickle) coordination mode,
tives of this type contain an ansa-chromocene ligands. This form 18-electron adducts with CO, PF3 , RNC, PPhMe2 , and
tetramethylethylene-bridged chromocene carbonyl complex, other two-electron donor ligands.89
[Me4 C2 (C5 H4 )]2 Cr(CO), is the product of the reaction of
the bis-Grignard reagent Me4 C2 (C5 H4 MgCl)2 4THF with
CrCl2 THF in a CO atmosphere.81 While extremely air sen- 5.7 Miscellaneous Compounds of Chromium(II)
sitive, this substance is sufficiently robust to be sublimed
The CrR2 fragment figures prominently in this group
at 60 70 C. Similarly, adducts of the type [trans-1,2-
of molecules. A thermally stable complex formulated
(3,4-(CH3 O)2 C6 H3 )2 C2 H2 {5 -C5 H4 }2 ]Cr(L) (L = CO, CNR)
as Cr(CH2 SiMe3 )2 was obtained from the interaction of
and Me2 Si(5 -C5 Me4 )2 Cr(CO) have been reported.82,83 At
Me3 SiCH2 Li with excess CrCl2 or CrCl3 . Its true tetrameric
elevated CO pressures, [Me4 C2 (C5 H4 )]2 Cr(CO) and (5 -
structure, Cr4 (CH2 SiMe3 )8 , was later revealed by X-ray
C5 H5 )2 Cr(CO) react reversibly to give dicarbonyl species
with concomitant 5 3 slippage of one of the cyclopen- crystallography.90 Treatment of trans-CrCl2 (dmpe)2 with two
tadienyl rings (Scheme 8). Surprisingly, even a ligand-free equivalents of MeLi yields the 16-electron trans dimethyl com-
ansa-chromocene, namely, Me2 Si(5 -C5 Me4 )2 Cr, has now plex, CrMe2 (dmpe)2 .91 Related (dialkyl)bisphosphine com-
been prepared and structurally characterized.84 pounds with a rare square-planar geometry, cis-CrR2 (dippe)
The known chromocene analogues feature substituted (R = Me3 CCH2 , Me3 SiCH2 , or 1,3,5-Me3 C6 H2 ; dippe =
cyclopentadienyl rings and/or other anionic ligands with pen- 1,2-bis(diisopropylphosphinoethane)) are synthesized by
tahapto coordination. (5 -C5 Me5 )2 Cr is efficiently prepared alkylation of dimeric [CrCl2 (dippe)]2 . An X-ray study showed
from [C5 Me5 ]Na and Cr2 (OAc)4 .85 This volatile, air-sensitive extremely long CrP bonds in these molecules, a consequence
solid is an extremely potent reducing agent (E>1/2 = of their high-spin d4 chromium centers ( = 4.9 B ), the trans
1.04 V), forming mildly air-sensitive [(5 -C5 Me5 )2 Cr]+ in influence of R, and the steric requirements of the R groups and
the presence of water, ammonium ion, or ferricinium ion. By phosphine. All of these dmpe and dippe products are air and
contrast, chromocene is inert to water and decomposed by [(5 - moisture sensitive; in spite of their electron-deficient config-
C5 H5 )2 Fe]+ ; chromocinium salts are extremely air sensitive, uration, none are agostic (see Agostic Bonding). As ethylene
even pyrophoric (see Section 6.9). Complexes with mono- polymerization catalysts, the dippe compounds demonstrate
substituted and perdeuterated cyclopentadienyl rings have little activity, which may imply that low-valent CrII centers
also been reported. Octaisopropylchromocene undergoes a are not the active sites in chromium-based catalytic processes.
low-spin/high-spin transition with increasing temperature.86 (5 -C5 Me5 )Cr(dmpe)Me is derived from the chemical
Structurally similar to and isoelectronic with chr- reduction of its CrIII analogue with Na/Hg. Air sensitive but
omocene are (5 -indenyl)2 Cr (now known to have thermally stable, its magnetic moment, 2.79 B , is compatible
a dinuclear structure)87 (5 -fluorenyl)2 Cr, and [5 -(9- with a low-spin d4 configuration.92 Attempts to perform similar
methyl)fluorenyl]2 Cr, (5 -C8 H11 )2 Cr, {[(3)-1,6-C2 B10 H12 ]2 chemistry on [(5 -C5 Me5 )Cr(dmpe)R]+ (R = Et, other alkyls)
Cr}2 , (5 -pentadienyl)2 Cr, and (5 -C5 R5 )Cr(5 -pentadienyl) were unsuccessful. This CrII complex reacted with ethylene
(R = H, Me). Control of the spin state by sterically at room temperature, but facile -elimination prevented the
formation of a polymer. That its isostructural CrIII analog
polymerized ethylene at 90 C implies that chromium(III)
is the more suitable oxidation state for catalysis, at least
in this system. Reaction of the ethylene polymerization
CO
catalyst [(5 -C5 Me5 )CrMe(THF)2 ]BPh4 with styrene gave
CO (5 -C5 Me5 )Cr(6 -Ph-BPh3 ), a CrII sandwich compound
Cr CO Cr
CO incorporating one of the rings of the noninteracting BPh4
counterion.
Alkylation of the dinuclear chloride precursor [(5 -
C5 Me5 )Cr(-Cl)]2 yields a series of alkyl bridged
Scheme 8 chromium(II) alkyls of the constitution [(5 -C5 Me5 )Cr(-R)]2
10 CHROMIUM: ORGANOMETALLIC CHEMISTRY
(R = Me, Et, n-Bu, CH2 SiMe3 , Ph). They feature short CrCr pentaaquo cations; a similar synthesis employs the isomeric
distances (2.26 A), low effective magnetic moments, and bromoalkylpyridinium bromides. Oxidation of CrII salts by
attenuated reactivity, all consistent with strong metal metal hydroperoxides and peroxides gives cationic products, as
bonding.93 Steric saturation of chromium with a sterically does the hydrolysis of RCrCl2 Sn . Finally, the interaction of
encumbered tris(pyrazolyl)borate ligand (i. e. Tpt -Bu,Me = CrII and alkylbis(dimethylglyoximato)cobalt also provides
hydrotris(3-tert-butyl-5-methylpyrazolyl)borate), on the other [RCr(OH2 )5 ]2+ . Most of these processes involve the
hand, facilitates the preparation of mononuclear, generation of a free radical and its subsequent attack on
coordinatively unsaturated alkyls. Tpt -Bu,Me CrR (R = Cl, chromium(II).
Et, Ph, CH2 SiMe3 ) adopt cis divacant octahedral structures Solutions of these cations have been prepared for numerous
and high-spin configurations with four unpaired electrons.94 ligands R, including CHCl2 , CF3 , CH2 OH, C(Me)2 OH, and
Notably, these four-coordinate 12-electron species do not react 5 -C5 H5 , but few have been isolated as solids. Like RCrCl2 Sn ,
with ethylene. However, Tpt -Bu,Me CrPh undergoes a clean these compounds are temperature and oxygen sensitive. In the
reaction with O2 , producing the paramagnetic CrIV complex presence of acid or mercury(II), CrR bond cleavage occurs
Tpt -Bu,Me Cr(O)OPh via an observable Cr(III) superoxide to give RH or RHgCl. Oxidative cleavage generates the
intermediate.95 aldehyde, RCHO. Reactions with metal salts, organic halides,
and halogens are also known.
among these are (CH2 =CHCH2 )3 Cr, (CH2 =C(Me)CH2 )3 Cr, strain in M3 [CrPh6 ] causes the extrusion of MPh to leave this
(MeCH=CHCH2 )3 Cr, (1-norcamphyl)3 Cr, and [(Me3 Si)2 pentaphenylchromate. Solvents like THF or DME facilitate
CH]3 Cr.100 the process. Treatment of CrCl3 (THF)3 with PhNa in
The R3 CrSn triaryl derivatives are generally stable at ether constitutes a formal synthesis. Tetra(organo)chromates
room temperature, whereas their alkyl analogs must often M[CrR4 ] are also known for R = aryl and are obtained from
be isolated and handled at low temperature. All undergo the reaction of CrCl2 , CrR2 , or CrCl3 with RLi. Penta- and
thermal fragmentations and rearrangements under appropriate hexaphenylchromates will also combine with CrCl3 to give
conditions. The CrC bond of a triaryl complex homolyzes tetraphenylchromates if DME is available to stabilize the
to give the arene and the biaryl; alternatively, a -to- products. The first structurally characterized representative
rearrangement occurs and bis( -arene)chromium forms. is Li(THF)4 [Cr(C6 Cl5 )4 ]. It adopts a pseudooctahedral
Fragmentation via reductive dimerization to give butadienes geometry, including two CrCl interactions besides the four
is observed in triallyl and vinyl species. Trialkyl compounds covalent CrC bonds.74
are characterized by homolytic Cr C bond cleavage and Of these three types of poly(organo)chromate anions,
by - and -Hydride Elimination, the products being only the hexaorgano species tolerates a variety of lig-
alkanes, alkenes, and chromium hydrides. The molecule [t- and types bound to chromium. Hexamethylchromate has
BuSi(CH2 PMe2 )3 ]Cr(n-Bu)3 demonstrates an extraordinary been reported,102 as well as an unusual spirocyclic com-
stability for a 15-electron trialkyl: its decomposition requires pound, Li3 [Cr(1,4-C4 H8 )3 ] (Et2 O)2.5 . Notable polyaryls
a temperature of 95 C (Scheme 9). This resistance to - include the tris(2,2 -biphenyl) compound and the hydride
elimination is attributed to the kinetically inert d3 configuration Li3 [CrH(Ph)5 ](Et2 O)3 . Collectively, poly(organo)chromates
and the chelating tripod phosphine ligand, the arms of which are thermally stable, but exceedingly sensitive to oxygen,
are less likely to dissociate for entropic reasons.101 While R3 Cr water, and protic media. An exception is found in the
and R3 CrSn do not themselves affect alkene isomerization or tetra(organo)chromates, which tend to form chromium(II)
catalytic hydrogenation, their chromium-based fragmentation dimers with loss of R R. Both CrII and CrIII species are
products have been shown to isomerize alkenes and act formed in the reactions of these compounds, which include
as hydrogenation catalysts. In addition, triallylchromium is fragmentation and ligand replacement.
known to function as a catalyst for the polymerization and X-ray crystal structures of Li3 [CrMe6 ](dioxane)3 and of
oligomerization of butadiene and other unsaturated molecules. Na2 [CrPh5 ](Et2 O)3 (THF) have been determined. The latter
The R3 CrSn and R3 Cr complexes exhibit magnetic is a distorted trigonal bipyramid; the former is octahedral,
moments that are in the range expected for chromium(III): with a remarkably long CrC bond distances (average =
3.53 3.98 B . They react readily with HgCl2 and I2 ; most 2.300(15) A).
are sensitive to oxygen and moisture. The chemistry of these
compounds with unsaturated substrates is extensive, and is
described in detail elsewhere. 6.6 Solvated Mono(5 -cyclopentadienyl)chromium
Compounds
BPh4
Me
Me HNEt3BPh4
Cr Cr Cr
Me THF O Me
Me O
Scheme 9
12 CHROMIUM: ORGANOMETALLIC CHEMISTRY
(5 -C5 H5 )CrH{P(OMe)3 }3 with CCl4 yields the phosphite- found mono-, di-, and trialkyl complexes of (5 -C5 H5 ) and (5 -
stabilized compound (5 -C5 H5 )CrCl2 {P(OMe)3 }. Analogous C5 Me5 ); these will be examined in turn. Much of the interest
THF-solvated (5 -C5 Me5 )CrX2 S species have been reported in these compounds centers on their role as catalysts for the
for X = Cl, Br, and I; however, their syntheses differ signif- polymerization, oligomerization, and selective trimerization
icantly. Besides solvent ligand exchange, two other reactions of ethylene.
of these air-sensitive organometallics have been studied. (5 - Monoalkyls of the form (5 -C5 R5 )Cr(R )(L)Cl (R =
C5 R5 )CrX2 (THF) (R = H, X = Br, I; R = Me, X = Cl, Br, H, R = Me or Et, L = py, PPh3 , Cl ; R = Me, R =
I) dimerizes upon heating to give [(5 -C5 R5 )CrX2 ]2 . Finally, Me or Et, L = py, PMe3 , 3,5-lutidine) are prepared by
the hydride (5 -C5 H5 )CrH{P(OMe)3 }3 , the starting material cleavage of the dimers [(5 -C5 R5 )Cr(R )(-Cl)]2 with the
for the preparation of (5 -C5 H5 )CrCl2 {P(OMe)3 } (see above), appropriate nucleophile, L. Cationic monoalkyls, [(5 -
is itself obtained from (5 -C5 H5 )CrCl2 (THF), NaBH4 , and C5 Me5 )CrL2 R]X (L = py, PMe3 , THF, MeCN, 3,5-lutidine;
P(OMe)3 . L2 = dmpe, dppe, bipy; R = Me, Et), are derived from
the same pentamethylcyclopentadienyl dimer or from (5 -
C5 Me5 )Cr(R )(L)Cl upon treatment with TlPF6 in the presence
6.7 Miscellaneous Unsolvated Mono(5 - of L. An alternative preparation of the bis(THF)(methyl)
cyclopentadienyl)chromium Compounds cation involves protonation of [(5 -C5 Me5 )Cr(Me)(-Me)]2
with HNEt3 BPh4 in THF (Scheme 9).
The unsolvated form of the dichloride described in the Monomers and dimers can also serve as starting materials
previous section may be synthesized from chromocene and for the synthesis of the dialkyls (5 -C5 R5 )Cr(R2 )L (R = H,
hexachlorocyclopentadiene or gaseous HCl,103 whereas the R = Me, Bn, CH2 SiMe3 , L = PMe3 , PEt3 ; R = Me, R =
bromide is best obtained by removal of the solvate from Me, L = PMe3 , py, THF). Treatment of (5 -C5 R5 )CrCl2 (PR3 )
(5 -C5 H5 )CrX2 (THF) in vacuo. The iodide is only available with two equivalents of alkyllithium or a Grignard reagent
as crude (5 -C5 H5 )CrI2 from the reaction of C3 H5 I with gives the desired product, as does the cleavage of [(5 -
[(5 -C5 H5 )Cr(CO)2 ]2 . Trichloride anions, [(5 -C5 R5 )CrX3 ] C5 Me5 )Cr(Me)(-Cl)]2 with alkyllithium in the presence of L.
(R = H, X = Cl, Br, I; R = Me, X = I), result when HX is (5 -C5 Me5 )Cr(Me)2 py can also be obtained from the addition
added to (5 -C5 R5 )2 Cr, followed by NH4 X. The lithium salt of of py to dimeric [(5 -C5 Me5 )Cr(Me)(-Me)]2 .
the trichloro anion has been crystallographically characterized. A particular subset of these ligated dialkyls are those
Treatment of Cr(acac)3 with C5 H5 MgBr leads to formation of in which the ligand is tethered to the cyclopentadienyl lig-
(5 -C5 H5 )CrBr(acac). and. Thus, chromacyclopentane and cycloheptane derivatives
An unprecedented insertion of nitrile into the stabilized by the (5 ;1 -Me4 C5 CH2 CH2 NMe2 ) ligand have
chromium alkyl bonds of dimers [(5 -C5 Me5 )Cr(- been prepared and their reactivity supports the intermedi-
Cl)R]2 led to the formation of the mononuclear - acy of such metallacycles in the catalytic trimerization of
diketiminato species (5 -C5 Me5 )Cr{[HNC(R)]2 CR }Cl (R = ethylene.107 A variety of donor-ligand-substituted cyclopen-
Me, Et; R = H, Me).104 This unusual reactivity tadienylchromium(III) complexes with amino and phosphino
has been attributed to the relatively high oxidation substituents has been prepared and screened for an ethylene
state and coordinative unsaturation of the starting polymerization activity.108,109
dimers and intermediates. Similar to the -diketiminato Two other interesting cyclopentadienyl alkyls are (5 -
complex in structure are (5 -C5 Me5 )Cr{[OC(Me)2 ]2 CH2 }py, C5 Me5 )Cr(CH2 SiMe3 )2 and [(5 -C5 Me5 )2 Cr2 (1 -CH2 Ph)(-
featuring a chelating bis(alkoxide) ligand, and (5 - 3 : 6 -CH2 Ph)]. The former is an unusual 13-electron species
C5 Me5 )Cr[OC(Me)2 CHC(Me)O]py, whose bidentate ligand whose coordinative unsaturation makes it an extremely
is a doubly deprotonated -hydroxy ketone.105 These effective catalyst for ethylene polymerization, and which
molecules are the products of the reactions of (5 - exhibits a rich thermal decomposition chemistry.110 The latter,
C5 Me5 )Cr(R)2 py (R = Me or O-t-Bu, respectively) with a mixed-valent complex exhibits ferromagnetic coupling
acetone. between the two chromium atoms and is a catalyst for the
polymerization of ethylene as well.111
Compounds in this class are characterized by thermal
6.8 Mono(5 -cyclopentadienyl)chromium Alkyl stability, crystallinity, and sensitivity to air and moisture.
Compounds Most possess 15-electron configurations and pseudooctahe-
dral coordination spheres. The isolation of ethyl derivatives
This class of organometallics originates from chemistry of demonstrates that -elimination is not facile in these CrIII
the chromium carbon bond developed only within the last alkyls.105 Also, evidence for agostic interactions is lacking.
two decades.105,106 Illustrative of this fact is the observation While the reactivity of the neutral complexes is limited to lig-
that a comprehensive reference published in 1982 makes and exchange, alkylation, and dimer formation, cationic [(5 -
no mention of compounds of chromium(III) bearing both C5 Me5 )CrL2 R]X is recognized as an efficient ethylene poly-
cyclopentadienyl and alkyl ligands.16 Within this class are merization catalyst, particularly where L = THF, R = Me,
CHROMIUM: ORGANOMETALLIC CHEMISTRY 13
and X = BPh4 . The PF6 analog is equally reactive; however, alkyls with a wide variety of ancillary ligands other
it is prone to decomposition by abstraction of fluoride from than cyclopentadienyls.114 For example, N ,N -disubstituted
the counterion and chloride from the CH2 Cl2 solvent, yielding -diketiminato (i.e. nacnac) complexes of chromium
polynuclear chromium complexes held together by fluoride have been alkylated and shown to catalyze ethylene
bridges. The most reactive of these cationic alkyls is the polymerization.115,116 Specifically, the cationic complex [(2,6-
exceedingly labile [(5 -C5 Me5 )Cr(OEt2 )2 CH2 SiMe3 ][B(3,6- i-PrPh)2 nacnacCr(OEt2 )Me][B(3,6-(CF3 )2 C6 H3 )4 ] catalyzes
(CF3 )2 C6 H3 )4 ];112 it even oligomerizes propene, despite the the polymerization of ethylene in the absence of any acti-
well-established selectivity of CpCr-catalysts for insertion of vators or cocatalysts and produces polyethylene of extremely
ethylene over -olefins.113 narrow polydispersity.117 Another set of ligands used to stabi-
lize CrIII alkyls are the N-substituted 1,3,5-triazacyclohexanes,
for example, in {(i-Pr)3 N3 (CH2 )3 }Cr(CH2 SiMe3 )2 Cl.118 Oxi-
6.9 Chromocinium Derivatives and Analogs dation of square-planar CrII precursors containing a tri-
The chromocinium ion, [(5 -C5 H5 )2 Cr]+ , results from the dentate aminophosphine ligand with alkyl halides gives
oxidation of chromocene by chemical or electrochemical alkyls of the type Cr(R)X[N(SiMe2 CH2 PPh2 )2 ] and
means. Allyl iodide is an efficient oxidant; however, the Cr(R)X[N(SiMe2 CH2 PPh2 )2 ] (R = Me, CH2 SiMe3 ; X = Cl,
pyrophoric iodide product is best converted to the BPh4 salt Br, I). These compounds are unusual examples of five-
or the reineckate, [Cr(SCN)4 (NH3 )2 ] , for ease of handling. coordinate CrIII complexes.119
In addition, the reactions of [(5 -C5 H5 )Cr(CO)3 ]2 with CCl4
or HX (X = Br, I) and with chromocene generate the ion
as [(5 -C5 H5 )2 Cr][(5 -C5 H5 )CrX3 ] and [(5 -C5 H5 )Cr][(5 -
C5 H5 )Cr(CO)3 ], respectively. Treatment of CrBr3 with 7 CHROMIUM(IV) ORGANOMETALLICS
C5 H5 Li gives (5 -C5 H5 )2 CrBr. Electrochemical oxidation
occurs reversibly with a half-wave potential of 0.67 V.
Chromocinium prepared by this route is stable in solution as 7.1 Tetraorganochromium Compounds
the PF6 salt.
The decamethylchromocinium ion, [(5 -C5 Me5 )2 Cr]+ , has The majority of chromium(IV) organometallics belong to
been isolated as the iodide from chromocene and HI. Further the family of homoleptic tetraalkyls and tetraaryls. These
reaction with HI forms the salt of the complex anion [(5 - compounds are generally prepared by one of two synthetic
C5 Me5 )2 Cr][(5 -C5 Me5 )CrI3 ]. routes. In the first, the chromium(III) precursor CrCl3 (THF)3
There exist analogs of the chromocinium ion in is reacted with four equivalents of alkyl- or aryllithium. If the
which the cyclopentadienyl rings are partly or wholly reaction is performed in pentane or ether, a disproportionation
replaced by dianionic carborane ligands. Dicarbollide reaction occurs and the tetrasubstituted product forms directly.
ions [(3)-1,2-C2 B9 H9 R2 ]2 (R2 = H2 , HMe, Me2 , HPh) In THF, however, the reaction yields Li[CrR4 ], which gives
and [(3)-1,7-C2 B9 H11 ]2 react with CrCl3 to give {[(3)- CrR4 upon oxidation; substitution of Grignard reagents for
1,2-C2 B9 H9 R2 ]2 Cr} and {[(3)-1,7-C2 B9 H11 ]2 Cr} . If the alkyllithiums gives comparable results in some cases. Direct
reaction is carried out in the presence of C5 H5 , one obtains conversion to CrR4 also occurs via the second route, in
the neutral mixed-sandwich complexes (5 -C5 H5 )Cr[(3)- which Cr(O-t-Bu)4 and four equivalents of alkyllithium are
1,2-C2 B9 H9 R2 ] and (5 -C5 H5 )Cr[(3)-1,7-C2 B9 H11 ]. The combined in pentane.
chromium(III) metallacarborane [(1,6-C2 B10 H12 )2 Cr] has Table 2 lists representative homoleptic tetraalkyls and
been prepared by chemical (Ag+ , H2 O2 ) or electrochemical aryls. Like all -bonded transition metal alkyls, these
oxidation of its CrII precursor. These dicarbollyl derivatives compounds are subject to decomposition via a variety of
of CrIII are stable in air and can be recrystallized routes. The absence of -hydrogen atoms in many of these
from aqueous solutions, and are unaffected by acid. molecules, however, eliminates potential decomposition path-
They do, however, decompose in the presence of an ways involving -hydride eliminations, thereby enhancing
aqueous base. Electrochemical data indicate that reduction the thermal stability of these species. In other tetraalkyls, -
is not reversible in these complexes. A crystal-structure hydrogens are present but geometric or steric factors impede
determination has been carried out on the cesium salt of the concerted elimination or abstraction process. An obvi-
{[(3)-1,2-C2 B9 H9 (Me)2 ]2 Cr} . Related to these sandwich ous example is tetrakis(l-norbornyl)chromium, which will not
compounds is trianionic [(B10 H10 CH)2 Cr]3 , which exhibits eliminate to give the bridgehead alkene. In spite of these
similar properties and reactivity. sources of stabilization, chromium carbon bond homolysis
remains a feasible fragmentation pathway.
6.10 Other Chromium(III) Organometallics General features of each molecule in Table 2 include a
magnetic moment of 2.6 3.0 B , appropriate for a CrIV com-
The search for chromium-based olefin polymeriza- plex with two unpaired electrons, and tetrahedral coordination;
tion catalysts has led to the exploration of chromium the crystal structures of Cr(CH2 SiMe3 )4 and Cr(CH2 CMe3 )4
14 CHROMIUM: ORGANOMETALLIC CHEMISTRY
have recently been determined.120 As a rule, these com- by standard routes. Other reactions include carbonyl
pounds show limited reactivity, and this is particularly the substitution and oxidative decomposition, thermal coupling
case for those in which the metal center is effectively shielded of carbynes to yield alkynes, and transfer of carbyne ligands
by bulky alkyl groups. However, supported tetraalkyls, for to cobalt to form (3 -methylidyne)nonacarbonyl tricobalt
example, Cr(CH2 SiMe3 )4 or Cr(CH2 CMe3 )4 on an inorganic complexes.
oxide carrier, function as very active catalysts for ethylene
polymerization. A detailed surface organometallic study of
the reaction of these two compounds with silica showed the 7.3 Chromocene Derivatives and Other Compounds of
formation of surface bound bis(alkyl)chromium fragments, Chromium(IV)
for example, (SiO)2 Cr(CH2 CMe3 )2 , which was transformed
into alkylidene (SiO)2 Cr(=CHCMe3 ) upon heating. The
A series of reports123 describes a number of substi-
latter species initiated the polymerization of ethylene.121
tuted chromocene derivatives obtained from the oxidative
addition of sulfur, selenium, and halogen reagents to (5 -
7.2 Chromium Carbonyl Carbynes122 C5 H5 )2 Cr. Air-stable (5 -C5 H5 )2 Cr(NCY)(YCN) and (5 -
C5 H5 )2 Cr(CN)(NCY) (Y = S, Se) were produced in the
An attempt to replace the methoxy group of reactions of chromocene with (YNC)2 and Y(CN)2 respec-
(CO)5 Cr(=C(Ph)OMe) with a halide (from BX3 ) led to tively. Addition of HN3 and CNN3 to (5 -C5 H5 )2 Cr gave
the unanticipated formation of the first carbyne complex rise to (5 -C5 H5 )2 Cr(N3 )2 with release of H2 , and to (5 -
(see Carbyne Complexes). This synthetic method, cleavage C5 H5 )2 Cr(CN)(N3 ), while treatment of (5 -C5 H5 )2 Cr with IX
of a carbene substituent by a Lewis acid, remains a good (X = Cl, Br) gave (5 -C5 H5 )2 CrIX. Notably, none of these
general route to these organometallics. Initially, the Lewis compounds have been structurally characterized.
acid coordinates strongly to an oxygen-, nitrogen-, or sulfur- There are now also some ansa-chromocene derivatives
containing group present on the carbene. The weakened
that feature tetravalent chromium. The first of these was
carbene carbon heteroatom bond then breaks, and a transient
the diamagnetic hydride [Me4 C2 (5 -C5 H4 )2 Cr(CO)H][B(3,5-
halocarbene intermediate forms. This decomposes to a cationic
(CF3 )2 C6 H3 )4 ]124 that was observed as a metastable
carbyne whose halide counterion displaces the trans carbonyl
intermediate in the protonation of Me4 C2 (C5 H4 )2 Cr(CO).
to yield the neutral product. However, if the carbene is
More recently, the stable cyanide [Me4 C2 (5 -C5 H4 ){5 -
substituted in the trans position with a good -donor such as
a phosphine, the cationic carbyne species is charge stabilized C5 H3 B(C6 F5 )3 }Cr(CN)CNXyl] has been structurally
and can be isolated. characterized.125
Crystal-structure determinations performed on chromium A triamidoamine ligand ((N3 N)3 = ((Me3 SiNCH2 CH2 )3
3
carbonyl carbynes indicate an average Cr C bond length of N) ) has facilitated the preparation of a new class of
1.70 A, ca. 0.2 A shorter than the average Cr C(carbonyl) chromium(IV) organometallics. Alkyls (N3 N)CrR (R = Me,
distance. An exception is seen in X(CO)4 CrC-NR2 , in n-Bu) as well as the hydride (N3 N)CrH have been
which the CrC bond is somewhat longer and the CN characterized by X-ray diffraction.126 The five-coordinate
bond somewhat shorter than expected. These findings molecules adopt high-spin d2 configuration.
are consistent with the presence of some double bond Other chromium(IV) organometallics include K3 [Cr(O2 )2
character. The CrCR bond angle is customarily very (CN)3 ] and 1,1 -commo-Cr[(2,3-SiMe3 )2 -2,3-C2 B4 H4 ]2 . The
close to linear, but structures bent up to 12 are known. latter is a diamagnetic carborane sandwich complex.
Chromium carbonyl carbynes are frequently employed as Diamagnetism has also been claimed for the compounds
starting materials for the synthesis of carbenes inaccessible (5 -C5 Me5 )Cr(Cl)(Br)Me and (5 -C5 Me5 )Cr(OPh)2 Me.
CHROMIUM: ORGANOMETALLIC CHEMISTRY 15
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