COORDINATION CHEMISTRY

STRUCTURES AND ISOMERS

 ELECTRONIC CONFIGURATION
Ground State:
Progressive filling of the 3d, 4d, and 5d orbitals

Exceptions:
ns1 (n-1)d5 rather than ns2 (n-1)d4
ns1 (n-1)d10 rather than ns2 (n-1)d9

Transition metal ions:

First in first out
TRENDS - IONIC Radii
 COORDINATION COMPOUNDS
 Coordination compounds –
compounds composed of a
metal atom or ion and one
or more ligands.
 [Co(Co(NH3)4(OH2)3]Br6
 Ligands usually donate
electrons to the metal
 Includes organometallic
compounds
Werner’s totally inorganic
optically active compound.
 WERNER’S COORDINATION CHEMISTRY
• Performed systematic studies to understand bonding in coordination
compounds.
– Organic bonding theory and simple ideas of ionic charges were not
sufficient.
• Two types of bonding
– Primary – positive charge of the metal ion is balanced by negative ions in
the compound.
– Secondary – molecules or ion (ligands) are attached directly to the metal
ion.
• Coordination sphere or complex ion.
• Look at complex on previous slide (primary and secondary)
 WERNER’S COORDINATION CHEMISTRY
• He largely studied compounds with four or six ligands.
– Octahedral and square-planar complexes.
• It was illustrated that a theory needed to account for bonds
between ligands and the metal.
– The number of bonds was commonly more than accepted
at that time.
• 18-electron rule.
• New theories arose to describe bonding.
– Valence bond, crystal field, and ligand field.
COORDINATION COMPOUNDS
COORDINATION COMPOUNDS
LIGANDS
LIGANDS
LIGANDS
 CHELATING LIGANDS
 Chelating ligands trisoxalatochromate(III) ion or just [Cr(ox)3]3-
(chelates) – ligands that
have two or more points
of attachment to the
metal atom or ion.
 Bidentate, tridentate,
tetra.., penta…, hexa…
(EDTA).
 A HEXADENTATE LIGAND, EDTA
• There are six points of
attachment to the calcium
metal.
– Octahedral-type geometry
ethylene diamine tetraacetic
acid (EDTA)

ethylenediaminetetraacetatocalcium ion or just [Ca(EDTA)]2-

LIGANDS
 NOMENCLATURE
• Coordination compounds that are ionic, the cation is named
first and separated by a space from the anion, as is the case
for all ionic compounds. The names of neutral coordination
complexes are written without spaces.

Na[PtCl3(NH3)]
Sodium amminetrichloroplatinate(II)
K2[CuBr4]
Potassium tetrabromocuprate(II)
 NOMENCLATURE

trans-[Co(en)2I(H2O)](NO3)2
trans-aquabis(ethylenediamine)iodocobalt(III) nitrate

mer-[Ru(PPh3)3Cl3]
mer-trichlorotris(triphenylphosphine)ruthenium(III)
 NOMENCLATURE
• The name of the coordination compound (neutral, cationic or
anionic) begins with the names of the ligands. The metal is
listed next, following in parentheses by the oxidation state of
the metal.
 NOMENCLATURE

When more than one of a given ligand is bound to the same

metal atom or ion, the number of such ligands is designated by
the following prefixes:
2 di 6 hexa 10 deca
3 tri 7 hepta 11 undeca
4 tetra 8 octa 12 dodeca
5 penta 9 nona
 NOMENCLATURE

However, when the name of the ligand in question already

contains one of these prefixes or ligands with complicated names
(generally ligand names that are three syllables or longer), then
a prefix from the following list is used instead:
2 bis 6 hexakis
3 tris 7 heptakis
4 tetrakis 8 octakis
5 pentakis 9 ennea
 NOMENCLATURE
Neutral ligands are given the same name as the uncoordinated molecule, but
with spaces omitted. Some examples are:
(CH3)3SO dimethylsulfoxide (DMSO)
(NH2)2CO urea
C5H5N pyridine
terpy terpyridine
bpy 2,2’-bipyridine
en ethylenediamine
PCl3 trichlorophosphine
PPh3 triphenylphopshine
 NOMENCLATURE

EXCEPTIONS: Some neutral molecules, when serving as ligands

are given special names. These are:
NH3 ammine
H2 O aqua
NO nitrosyl
CO carbonyl
CS thiocarbonyl
 NOMENCLATURE
• Anionic ligands are given names that end in the letter “o”.
When the name of the free, uncoordinated anion ends in
“ate”, the ligand name is changed to end in “ato”. Some
examples are :
CH3CO2- (acetate) acetato
SO42- (sulfate) sulfato
CO32- (carbonate) carbonato
acac acetylacetonato
 NOMENCLATURE

When the name of the free, uncoordinated anion ends in “ide”,

the ligand name is changed to end in “ido”. Some examples are:
N3- (nitride) nitrido
N3- (azide) azido
NH2- (amide) amido
 NOMENCLATURE

When the name of the free, uncoordinated anion ends in “ite”,

the ligand name is changed to end in “ito”. Some examples are:
NO2- (nitrite) nitrito
SO32- (sulfite) sulfito
ClO3- (chlorite) chlorito
 NOMENCLATURE
Certain anionic ligands are given special names, all ending in “o”:
CN- cyano F- fluoro
Cl- chloro Br- bromo
I- iodo O2- oxo
O2- superoxo OH- hydroxo
H- hydrido CH3O- methoxo
 NOMENCLATURE

The ligands are named alphabetically, ignoring the prefixes bis,

tris, etc…
 NOMENCLATURE
When the coordination entity is either neutral or cationic, the
usual name of the metal is used, followed in parentheses by the
oxidation state of the metal. However, when the coordination
entity is an anion, the name of the metal is altered to end in
“ate”. This is done for some metals by simply changing the
ending “ium” to “ate”:
Scandium scandate
Titanium titanate
Chromium chromate
 NOMENCLATURE

Geometrical isomers are designated by cis- or trans- and mer- or

fac-, the latter two standing for meridional or facial, respectively.
 NOMENCLATURE
Bridging ligands are designated with the prefix -. When there
are two bridging ligands of the same kind, the prefix di-- is
used. Bridging ligands are listed in order with other ligands, and
set off between hypens. An important exception arises when the
molecule is symmetrical, and a more compact name can be given
by listing the bridging ligand first.
 NOMENCLATURE

Example:
NOMENCLATURE
NOMENCLATURE
NOMENCLATURE
 NOMENCLATURE

Ligands that are capable of linkage isomerism are given specific

names for each mode of attachment.
-SCN- thiocyanato (S-thiocyanato)
-NCS- isothiocyanto (N-thiocyanto)
-NCSe- isoselenocyanato (N-selenocyanato)
-NO2- nitro
-ONO- nitrito
 EXAMPLES

1. [Co(NH3)5CO3]Cl
2. Potassium pentachloronitridoosmate(VI)
3. [Cr(H2O)4Cl2]Cl
4. Potassium pentacyanonitrosylferrate(II)
5. K4[Mn(CN)6]
6. [Ni(bipy)3(NO3)2]
7. [Co(N3)(NH3)5]SO4
 NOMENCLATURE
• Bridging ligands between two metal ions have the prefix ‘ ’.
– -amido--hydroxobis(tetraamminecobalt)(IV)
ISOMERISM
ISOMERISM
 ISOMERISM
• Four-coordinate complexes
– Square-planar complexes may have
cis and trans isomers. No chiral
isomers (enantiomers) are possible
when the molecule has a mirror
plane.
– cis- and trans-
diamminedichloroplatinum(II)
– How about tetrahedral complexes?
– Chelate rings commonly impose a
‘cis’ structure. Why
ISOMERISM
ISOMERISM
 CHIRALITY
• Mirror images are nonsuperimposable.
• A molecule can be chiral if it has no rotation-reflection axes (S n)
• Chiral molecules have no symmetry elements or only have an
axes of proper rotation (Cn).
– CBrClFI, Tetrahedral molecule (different ligands)
– Octahedral molecules with bidentate or higher chelating
ligands
– Octahedral species with [Ma2b2c2], [Mabc2d2], [Mabcd3],
[Mabcde2], or [Mabcdef]
CHIRALITY
 SIX-COORDINATE OCTAHEDRAL COMPLEXES

 ML3L3’
 Fac isomers have three
identical ligands on the
same face.
 Mer isomers have three
identical ligands in a
plane bisecting the
molecule.
ISOMERISM
 SIX-COORDINATE OCTAHEDRAL COMPLEXES
 The maximum number of isomers can be difficult
to calculate (repeats).
 Placing a pair of ligands in the notation <ab>
indicates that a and b are trans to each other.
 [M<ab><cd><ef>], [Pt<pyNH3><NO2Cl><BrI>]
 How many diastereoisomers in the above
platinum compound (not mirror images)?
 Identify all isomers belonging to Ma3bcd.
 COMBINATIONS OF CHELATE RINGS
• Propellers and helices
– Left- and right-handed propellers
• Examine the movement of a propeller required to move it in a
certain direction.
– For a left-handed propeller, rotating it ccw would cause it
to move away ().
– For a right-handed propeller, rotating it cw would cause it
to move away ().
This is called ‘handedness’. Many molecules possess it.
 Tris(ethylenediamine)cobalt(III)
• this molecule can be treated like a three-bladed propeller.
• look down a three fold axis to determine the ‘handedness’
of this complex ion.
– the direction of rotation required to pull the
molecule away from you determines the
handedness ( or ).
• do this with you molecule set and rubber bands.
 DETERMINING HANDEDNESS FOR CHIRAL
MOLECULES
• Complexes with two or more nonadjacent chelate rings may have
chiral character.
– Any two noncoplanar and nonadjacent chelate rings can be used.
– Look at Figure 9-14 (Miessler and Tarr).
• Molecules with more than one pair of rings may require more than
one label.
– Ca(EDTA)2+
• Three labels would be required.
• Remember that the chelate rings must be noncoplanar,
nonadjacent, and not connected at the same atom.
 LINKAGE (AMBIDENTATE) ISOMERISM
 A few ligands may bond to the metal through different atoms.
 SCN- and NO2-
 How would you expect hard acids to bond to the thiocyanate
ligand?
 Solvents can also influence bonding.
 High and low dielectric constants.
 Steric effects of linkage isomerism
 Intramolecular conversion between linkages.
 [Co(NH3)5NO2]+2, Figure 9-19.
 COORDINATION NUMBERS AND STRUCTURES

• Factors considered when determining structures.

– The number of bonds. Bond formation is exothermic; the
more the better.
– VSEPR arguments
– Occupancy of d orbitals.
– Steric interference by large ligands.
– Crystal packing effect.
It may be difficult to predict shapes.
 LOW COORDINATION NUMBERS (C.N.)
• CN 1 is rare except in ion pairs in the gas phase.
• CN 2 is also rare.
– [Ag(NH3)2]+, Ag is d10 (how?)
– VSEPR predicts a linear structure.
– Large ligands help force a linear or near-linear arrangment.
• [Mn(N[SiMePh2]2)2] in Figure 9-22.
• C.N. 3 is more likely with d10 ions.
– Trigonal-planar structure is the most common.
– [Cu(SPPh3)3]+, adopts a low C.N. due to ligand crowding.
 COORDINATION NUMBER 4

• Tetrahedral and square planar complexes are the most

common.
– Small ions and/or large ligands prevent high coordination
numbers (Mn(VII) or Cr(VI)).
• Many d0 or d10 complexes have tetrahedral structures (only
consider bonds).
– MnO4- and [Ni(CO)4]
– Jahn-Teller distortion (Chapter 10)
 COORDINATION NUMBER 4
• Square-planar geometry
– d8 ions (Ni(II), Pd(II), and Pt(III))
• [Pt(NH3)2Cl2]
– The energy difference between square-planar and
tetrahedral structures can be quite small.
• Can depend on both the ligand and counterion.
• More in chapter 10.
 COORDINATION NUMBER 5
• Common structures are trigonal bipyramid and square
pyramid.
– The energy difference between the two is small. In many
measurements, the five ligands appear identical due to
fluxional behavior.
– How would you modify the experiment to differentiate
between the two structures?
• Five-coordinate compounds are known for the full range of
transition metals.
– Figure 9-27.
 COORDINATION NUMBER 6
• This is the most common C.N. with the most common
structure being octahedral.
– If the d electrons are ignored, this is the predicted shape.
• [Co(en)3]3+
• This C.N. exists for all transition metals (d0 to d10).
 DISTORTIONS OF COMPLEXES CONTAINING C.N.
6
• Elongation and compression (Fig. 9-29).
– Produces a trigonal antiprism structure when the angle
between the top and bottom triangular faces is 60.
– Trigonal prism structures are produced when the faces are
eclipsed.
• Most trigonal prismatic complexes have three bidentate
ligands (Figure 9-30).
•  interactions may stabilize some of these structures.
The Jahn-Teller effect is useful in predicting observed distortions.
 HIGHER COORDINATION NUMBERS
• C.N. 7 is not common
• C.N. 8
– There are many 8-coordinate complexes for large
transition elements.
• Square antiprism and dodecahedron
• C.N.’s up to 16 have been observed.
 MAGNETIC SUSCEPTIBILITY

• Diamagnetic versus paramagnetic complexes.

• Commonly provides mass susceptibility per gram.
• Magnetic moment 
1
  2.828( T ) 2
  magnetic susceptibility
 CONTRIBUTIONS TO THE MAGNETIC MOMENT

• Spin magnetic moment

– S = maximum total spin in the complex
• O atom
• Orbital angular momentum
– Characterized by the quantum number L which is equal the
maximum possible sum of ml values.
• O atom

 S  L  g [ S ( S  1)]  [ 1 4 L( L  1)]
 CONTRIBUTIONS TO THE MAGNETIC MOMENT

• Usually, the spin-only moment is sufficient to

calculate the magnetic moment.
– Especially for the first transition series
 S  g S(S  1) or n ( n  2)

where g (gyromagnetic ratio) is approximated to be 2

and n is the number of unpaired electrons.
– Determine the spin-only and complete magnetic moment
for Fe.
Calculate the spin-only magnetic moment

For the following atoms/ions:

Fe+2 (observed: 5.1), Fe, Cr, Cr+3 (observed =

3.8)
 ELECTRONIC SPECTRA

• Orbital energy levels can be obtained directly from

electron spectra (will be covered later).

• This chapter illustrates simple energy level diagrams

that are commonly more complex.

• Based upon subtle differences in electronic spectra, the

structure may be predicted with some success.
 THEORIES OF ELECTRONIC STRUCTURE
• Valence Bond Theory – Not commonly used, but the hybrid notation is
still common.

• Crystal Field Theory – An electrostatic approach used to describe the

splitting in metal d-orbital energies. Does not describe bonding.

• Ligand Field Theory – A more complete description of bonding in terms

of the electronic energy levels of the frontier orbitals. Commonly does
not include energy of the bonding orbitals.

• Angular Overlap Method – Used to estimate the relative magnitude of

the orbital energies in a MO calculation.
 VALENCE BOND THEORY (HYBRIDIZATION)
• A set of hybrid orbitals is produced to explain the bonding.
– Octahedral – d2sp3 (6 hybrid orbitals of equal energy)
– Tetrahedral - ??

• Uses ‘inner’ and ‘outer’ orbitals to explain the

experimentally determined unpaired electrons.
– The magnetic behavior determines which d orbitals (e.g. 3d or 4d) are used
for bonding (Figure 10-2).
 VALENCE BOND DESCRIPTION
• Two configurations are possible for d4-d7 ions.
• Fe(III) has 5 electrons in the d-orbitals.
– One unpaired electron, the ligands are ‘strong’ and force the
metal d electrons to pair up.
• Strong-field (bind strongly)  low spin complex
• The hybridization orginates from the 3d inner orbitals
(d2sp3).
 VALENCE BOND DESCRIPTION
– Five unpaired electrons, the ligands are ‘weak’ and cannot
force the metal d electrons to pair up.

• Weak-field (bind weakly) high spin

• The hybridization originates from the 4d outer orbitals
(sp3d2).
 VALENCE BOND THEORY

Structure, hybridization, and magnetism

1)[Co(NH3)6]3+, diamagnetic, octahedral
2)[CoF6]3-, paramagnetic, octahedral
3)[PtCl4]2-, diamagnetic, sq. planar
4)[NiCl4]2-, pamagnetic, tetrahedral
 SAMPLE PROBLEM:

• The complexes [Mn(H2O)6]2+, [Fe(H2O)6]3+,

[MnCl4]2-, and [FeCl4]- have all magnetic
moments. What does this tell about the
geometric and electronic structures of these
complexes?
 CRYSTAL FIELD THEORY

• Focus: energies of the d orbitals

• Assumptions
1. Ligands: negative point charges
2. Metal-ligand bonding: entirely ionic

strong-field (low-spin): large splitting of d orbitals

weak-field (high-spin): small splitting of d orbitals
20_454

eg(d z2, d x 2 – y 2)


t2g (d xz, d yz, d xy)

 = crystal field splitting

Free metal ion

3d orbital
energies
High spin Low spin
 CRYSTAL FIELD THEORY
• The average energy of the d-orbitals in the presence of the
octahedral field is greater than than of the free ion.

• Energy difference between the two sets is equal to O.

– The t2g set is lowered by 0.4 O and the eg set is raised by 0.6 O.

• Crystal field stabilization energy (CFSE) – The energy difference

between the actual distribution of electrons and that for all electrons
in the uniform field.
– Equal to LFSE (later)

• Drawbacks
 LIGAND FIELD THEORY – OCTAHEDRAL COMPLEXES
• Consider -type bonding between the ligands and the metal
atom/ion.
• Construct LGOs (performed previously).
– What is the reducible representation?
– Construct the LGOs (pictures).
• Construct the molecular orbitals with the metal orbitals.
– Same symmetry types.
• A group of metal orbitals do not have the appropriate
symmetry?
– Which orbitals are these? Symmetry type? Bonding?
• Look at Figure 10-5.
 SF6

= A1g + T1u + Eg
 LIGAND FIELD THEORY – OCTAHEDRAL
COMPLEXES

• The six bonding orbitals are largely filled by the

electrons from the ligands.
• The higher MOs (e.g. t2g and eg) are largely filled by the
electrons on the metal atom/ion.
– The ligand field treatment largely focuses on the t2g and
higher orbitals.
• The split between the two sets of orbitals, t 2g and eg, is
called O.
 LIGAND FIELD THEORY – OCTAHEDRAL
COMPLEXES
• Ligands whose orbitals interact strongly with the metal
orbitals are called strong-field ligands.
– Strong-field  large O  low spin (why?)
• Ligands with small interactions are called weak-field
ligands.
– Weak-field  small O  high spin (why?)
• For d0 – d3 and d8-d10 only one electron configuration is
possible (no difference in net spin).
• For d4 – d7 there is a difference between strong- and weak-
field cases.
 LOW SPIN VERSUS HIGH SPIN

• Energy of pairing electrons

  c  e
– c is the Coulombic energy of repulsion (always positive
when pairing) and e is the quantum mechanical
exchange energy (always negative).
• e relates to the number of exchangeable pairs in a particular
electron configuration. This term is negative and depends on the
number of possible states.
Determine c and e for a d5 metal complex (low and high spin).
 LOW SPIN VERSUS HIGH SPIN

• The relationship between O, c, and e determines the

orbital configuration.
•  is largely independent on the ligands while O is
strongly dependent.
• Look at Table 10-6 which gives these parameters for
aqueous (aqua) ions.
– O for 3+ ions is larger than O for 2+ ions.
– O values for d5 are smaller than d4 and d6.
 LOW SPIN VERSUS HIGH SPIN

• If O>, there is a lower energy upon pairing

in the lower levels (low spin).
• If O<, there is a lower energy with unpaired
electrons in the lower levels (high spin).
• In Table 10-6, [Co(H2O)6]3+ is probably the only
complex that could be low spin.
 Ligand Field Stabilization Energies (LFSE)

• The difference (1) the total energy of a coordination

complex with the electron configuration resulting
from ligand field splitting of the orbitals and (2) the
total energy for the same complex with all the
orbitals equally populated is the LFSE.
• -2/5O + 3/5O (d4 to d7 complexes)
• Table 10-7
  BONDING IN OCTAHEDRAL COMPLEXES

• The x and z axes must be taken as a single set

producing a combined LGO set. Why?
• Be able to derive the reducible representation.
–  = T1g + T2g + T1u + T2u
• How will the LGOs combine with orbitals from the
metal atom/ion?
• Discuss the overlap between the -bonding LGOs
and the p-orbitals of T1u symmetry.
 PI BONDING IN OCTAHEDRAL COMPLEXES

• The main addition to the interaction diagram

is between the t2g orbitals of the metal and
LGOs.
– These were nonbonding when only considering -
type bonding (look at Figure 10-5).
• Pi bonding may occur when the ligands have
available p or * molecular orbitals.
 LIGANDS WITH EMPTY * ORBITALS

• Examine the example for the CN- ligand in the book

(Figure 10-9).
• The HOMO forms the LGOs from -type bonding
(already discussed previously).
• The LUMO, 1*, also forms a reducible set of LGOs
(T1g + T2g + T1u + T2u).
– Examine Figure 10-10 to illustrate effectiveness of overlap.
 LIGANDS WITH EMPTY * ORBITALS
• The resulting t2g LGOs are generally higher in energy
than the initial t2g orbitals on he metal.
– Bonding/antibonding t2g orbitals will result.
– What will this do to O and the bond strength?
• Figure 10-11.
• This is termed as metal-to-ligand  bonding or 
back-bonding.
– Some of the electron density in the d orbitals on the metal
is donated back to the ligands.
– The ligands are termed as -acceptor ligands.
 LIGANDS WITH FILLED -TYPE ORBITALS

• Ligands such as F- or Cl- will possess molecular 

orbitals that possess electrons.
• This set of ‘t2g’ orbitals are generally lower in
energy than the t2g orbitals on the metal.
• What are the consequences?
– Examine Figure 10-11.
• Ligand-to-metal  bonding (-donor ligands).
– This bonding is generally less favorable.
 SQUARE-PLANAR COMPLEXES

• The y-axis is pointed toward the center atom.

– LGOs for sigma-type bonding.
• The -bonding orbitals on the x- and z-axes have to be
considered separately? Why?
– These are termed as  (px) and  (pz)
• Examine Table 10-9.
– What is the symmetry of a square-planar complex?
 SQUARE-PLANAR COMPLEXES
SIGMA-TYPE BONDING ONLY
• Finding the LGOs.
– red = A1g + B1g + Eu
• What are the orbitals on the central metal atom that
can interact with these LGOs?
• Inspecting the character table reveals that the metal
d-orbitals are split into three representations. Why?
• Examine Figure 10-13.
– The energy difference between the eg/b2g nonbonding
orbitals and the a1g antibonding is .
 SQUARE-PLANAR COMPLEXES
INCLUDING PI-BONDING
• px = A2g + B2g + Eu ()
– What are the interacting orbitals on the metal?
• pz = A2u + B2u + Eg ()
– What are the interacting orbitals on the metal?
• The effective overlap of the p orbitals on the
metal to form  bonds is small.
• Examine Figure 10-15.
 THE ‘SETS’ OF ORBITALS IN FIGURE 10-15
• The 1st set contains bonding orbitals (mostly sigma).
– 8 electrons from the ligands largely fill these orbitals.
• The 2nd set contains 8 -donor orbitals of the ligands.
– This interaction is small and decreases the energy differences in orbitals
the next higher set.
• The 3rd set is primarily metal d-orbitals with some modifications
due to interactions with the ligands.
– 3, 2, and 1 are in this set.
• The 4th set largely originates from the * orbitals of the ligands
(if present).
– One of the main effects of these orbitals is the increase in the gap energy
labeled 1.
 ANGULAR OVERLAP (CRYSTAL FIELD)

• Estimates the strength of interaction between individual ligand

orbitals and d-orbitals based on the overlap between them.
These values are then combined for all ligands and d-orbitals.
• The value for a given d-orbital is the sum of the numbers for the
appropriate ligands in a column.
– This number can be positive or negative depending on location of the
ligand and d-orbitals.
• The value for a given ligand is the sum of the numbers for all d-
orbitals in the row.
– This number can also be positive or negative depending on location of the
ligand and d-orbitals.
 ANGULAR OVERLAP

• Sigma-donor interaction (no pi-orbitals are available).

– [M(NH3)6]n+
• The strongest interaction is between the metal dz2
orbital and a ligand p-orbital (or appropriate MO).
• Describe the interaction based on this method.
– Table 10-11 and Figure 10-20.
 ANGULAR OVERLAP
• Pi-acceptor ligands (available -type orbitals).
• Strongest interaction is between dxz and * on the ligand.
• The * orbitals are almost always higher in energy.
– Reverse the signs.
• Figure 10-22 and Table 10-12
– There is a lowering of 4e due to this interaction.
• Why is magnitude e always smaller than that of e?
• Understand -donor interactions.
SAMPLE PROBLEM

Using the angular overlap model, determine

the splitting pattern of the d orbitals for a
tetrahedral complex of formula ML4.where L is
a capable of  interactions only.
 SAMPLE PROBLEM

Determine the energies of the d orbitals

predicted by the angular overlap model for
square planar complexes
a) considering  interactions only
b) considering both -donor and -
acceptor interactions
 THE SPECTROCHEMICAL SERIES

•  depends on the relative energies and the

degree of overlap.
• How ligands effect 
– -donor ligands
– -donating
– -accepting (or back bonding)
• Understand the spectrochemical series (page
368)
 MAGNITUDE OF E, E, AND 

• Changing the metal and/or ligand effects the magnitudes of

e and e, thereby changing the value of .
– Aqua species of Co2+ and Co3+
– [Fe(H2O)6]2+ versus [Fe(H2O)6]3+
• Tables 10-13 and 10-14 (Angular Overlap)
– e > e (always)
– Values decrease with increasing size and decreasing
electronegativity
– Negative values for e. Why?
 THE JAHN TELLER EFFECT

• There cannot be unequal occupation of orbitals

with identical energies. The molecule will distort
so that these orbitals are no longer degenerate.
– Cu(II) d9 ion, The complex will distort. How?
– The low-spin Cr(II) complex is octahedral with
tetragonal distortion (Oh  D4h)
• Two absorption bands are observed instead of one.
 DETERMINING FOUR- AND SIX-COORDINATE
PREFERENCES

• General angular overlap calculations of the energies

expected for different number of d electrons and
different geometries can give us some indication of
relative stabilities.
– Larger number of bonds usually make the octahedral
complexes more stable. Why are the energies equal in the
d5, d6, and d7 cases?
– Figure 10-27.
 DETERMINING FOUR- AND SIX-COORDINATE
PREFERENCES

• The success of these simplistic calculations is

variable.
– The s- and p-orbitals of the metal are not included.
– No -type interactions are included in Figure 10-27.
– The orbital potential energies for the metals change
with increasing atomic number (more negative).
• Can add –0.3e  (increase in Z) as a rough correction to
the total enthalpy.
 THE PROCESS FOR A COMPLEX OF D3h
SYMMETRY
• Construct the sigma-type bonding LGOs for the
complex.
• Determine the interacting orbitals on the center atom.
• Construct a table to determine e (and e if
appropriate).
• Construct the MO diagram and overlap energy figure.
Homework: Determine the e contribution.
 Symmetry and Group Theory

The symmetry properties of molecules and how they can be used

to predict vibrational spectra, hybridization, optical activity, etc.
 POINT GROUPS

Molecules are classified and grouped based

on their symmetry. Molecules with similar
symmetry are but into the same point group.

A point group contains all objects that have

the same symmetry elements.
 SYMMETRY ELEMENTS

Symmetry elements are mirror planes, axis of

rotation, centers of inversion, etc.

A molecule has a given symmetry element if the

operation leaves the molecule appearing as if
nothing has changed (even though atoms and bonds
may have been moved.)
Element Symmetry Operation Symbol
Symmetry Elements
Identity E
n-fold axis Rotation by 2π/n
Cn
Mirror plane Reflection
σ
Center of inversion Inversion i
n-fold axis of Rotation by 2π/n Sn
improper rotation followed by reflection
perpendicular to the
axis of rotation
C3
C3 or three-fold rotational axis of the
ammonia molecule. If we rotate the ammonia
molecule by 360/3 or 120º about this
axis, its appearance is unchanged.
 Rotational axes of BF3
principal axis
(highest value of Cn)
C3 C3 C2 C2

three-fold axis three-fold axis two-fold axis two-fold axis

viewed from viewed from viewed from viewed from
above the side the side above

Note: there are 3 C2 axes

 SAMPLE PROBLEM
• How many axes of rotation does borazine
possess?
H
• Ethane in the eclipsed conformation?
H N H
B B

N N
H B H

H
 Mirror planes (σ) of BF3:
Mirror planes can contain the principal axis (σv) or be at right angles
to it (σh). BF3 has one σh and three σv planes: (v = vertical, h =
horizontal)
σv σh
mirror plane C3 mirror plane
principal axis C3
principal axis

σv mirror plane σh mirror plane

contains the C3 axis is at right angles to the C axis
 SAMPLE PROBLEM

• Mirror planes of symmetry for Borazine,

naphtlalene, diborane, dxy orbital?
 center of symmetry
center of symmetry

(Note: The center of symmetry is important in deciding whether orbitals

are g or u (lecture 2.))
 SAMPLE PROBLEM

• Which of the following flourine compounds

has center of inversion? BF3, SiF4, PF5, XeF5-,
SF6, C2F4,
 rotate
by 360o/4

The S improper rotation axis here is also a C axis

 Rotational axes and mirror planes of the water molecule:

C2 σv σv
C2 C2
principal axis
mirror plane mirror plane

The water molecule has only one rotational axis, its C2 axis,
which is also its principal axis. It has two mirror planes that
contain the principal axis, which are therefore σv planes. It
has no σh mirror plane, and no center of symmetry.
 Rotational axes and mirror planes of benzene
C
6
C2
principal axis C2

C2 C2
C6 σh
σv σv

C6
principal axis
C6
principal axis
 Rotational axes and mirror planes of boron trifluoride

C3 C2
principal axis
C2 C2

σh
σv σv
σh

boron trifluoride has a C3 principal C3

axis and three C2 axes, a σh mirror plane principal axis
three σv mirror planes, but no center of inversion
 Identity, E

All molecules have Identity. This operation

leaves the entire molecule unchanged. A
highly asymmetric molecule such as a
tetrahedral carbon with 4 different groups
attached has only identity, and no other
symmetry elements.
 Improper Rotation
An improper rotation is rotation, followed
by reflection in the plane perpendicular to the
axis of rotation.
 Improper Rotation
The staggered
conformation of
ethane has an S6 axis
that goes through
both carbon atoms.
 Improper Rotation

Note that an S1
axis doesn’t exist; it
is same as a mirror
plane.
 Improper Rotation

Likewise, an S2
axis is a center of
inversion.
 Sample problem

Draw the structure for the following showing the correct

geometry and identify all the symmetry elements present in each:

a) SCN- b) S2O32-, c) IF4- d) 1,8-dichloronaphthalene e)

formaldehyde
 Point Groups
Molecules with the same symmetry
elements are placed into point groups.

Group theory, the mathematical treatment of

the properties of groups can be used to
determine the molecular orbitals, vibrations,
and other properties of the molecule.
∞ ∞
 Point Groups
In general, you will not need to assign a
molecule to its point group. Recognition of
the features of some common point groups is
useful.
Point Groups
Water and ammonia
both belong to the Cnv
class of molecules.
These have vertical
planes of reflection,
but no horizontal
planes.
Point Groups
Y
The Dnh groups have a
X
horizontal plane in X
addition to vertical
planes. Many X
X
inorganic complexes
belong to these Y

symmetry groups.
 POINT GROUPS

Highly symmetrical molecules, such as

identically substituted tetrahedrons or
octahedrons belong to their own point groups
(Td or Oh respectively).
 Point Groups
In assigning a point group, we typically
ignore the fine detail, such as conformation
isomers, of the ligands.
In working problems using group theory,
the point group of the molecule will usually be
provided to you.
 Example:
• PF5, SF6, IOF3, XeF4, ethane (eclipsed and
staggered), ethylene and chloroethylene.
Ferrocene (eclipsed and staggered)
COORDINATION
CHEMISTRY III:
REACTIONS OF METAL
COMPLEXES

The ability to predict products and choose

appropriate reaction condition to obtain
the desired products is still a matter of art
as well as science.
substitution reactions
kinetic consequences of reaction pathways
experimental evidence in octahedral substitution
substitution reactions of square-planar complexes
the trans effect
oxidation-reduction reactions
reactions of coordinated ligand
SUBSTITUTION REACTIONS
SUBSTITUTION REACTIONS
MLn + L' MLn-1L' + L

Labile complexes <==> Fast substitution reactions (< few min)

Inert complexes <==> Slow substitution reactions (>h)
a kinetic concept

Not to be confused with

stable and unstable (a thermodynamic concept Gf <0)

Inert Intermediate Labile

d3, low spin d4-d6& d8 d8 (high spin) d1, d2, low spin d4-d6& d7-d10
SUBSTITUTION REACTIONS – INERT AND LABILE

INERT, LABILE vs STABLE,

UNSTABLE

kinetic terms thermodynamic terms

Stable but labile

unstable but inert

MECHANISMS OF LIGAND EXCHANGE REACTIONS
IN OCTAHEDRAL COMPLEXES
MLn X + Y MLn Y + X

Dissociative (D) Associative (A)

MLn X MLn Y MLn X MLn Y

X MLn Y Y X
MLn XY

Interchange (I)
MLn X MLn Y

Y X
[MLn]°

Ia if association X Y Id if dissociation
is more important is more important
 KINETICS
OF DISSOCIATIVE
REACTIONS
 Kinetics Fast equilibrium
K1 = k1/k-1
of interchange
reactions
k2 << k-1

For [Y] >> [ML5X]

Kinetics of associative reactions
Principal mechanisms of ligand exchange in octahedral complexes

Dissociative
k1
ML5 X ML5 + X
slow r = k 1 [ML5X]
+Y k2
ML5 Y
fast

Associative
k1
ML5 X + Y ML5 XY
slow r = k 1 [ML5X][Y]
-X k2
ML5 Y
fast
 Dissociative pathway
(5-coordinated intermediate)

MOST COMMON

Associative pathway
(7-coordinated intermediate)
Experimental evidence for dissociative mechanisms

Rate is independent of the nature of L

Experimental evidence for dissociative mechanisms

Rate is dependent on the nature of L

 Inert and labile complexes
Some common thermodynamic and kinetic profiles

Exothermic Exothermic Endothermic

(favored, large K) (favored, large K) (disfavored, small K)
Large Ea, slow reaction Large Ea, slow reaction Small Ea, fast reaction
Stable intermediate
 Labile or inert?
L
L L
M
L L

Ea L
L L
L M
L L L L
M X
L L
X G

LFAE = LFSE(sq pyr) - LFSE(oct)

 Why are some configurations inert and some are labile?

Inert !
Other metal on factors that affect reaction rates
Oxidation state of the central atom: Central atom with higher
oxidation states have slower ligand exchange rates

[AlF6]- > [SiF6]- > [PF6]- > SF6

Ionic radius. Smaller ions have slower exchange rates

[Sr(H2O)6]2+ > [Ca(H2O)6]2+ > [Mg(H2O)6]2+
112 pm 99 pm 66 pm

Both effects due to higher electrostatic attraction between

central atom and attached ligands.
Substitution reactions in square-planar complexes
the trans effect
L X L Y
+X, -Y
M M
T L T L

(the ability of T to labilize X)

Synthetic applications
of the trans effect
Mechanisms of ligand exchange reactions in square planar
complexes
L L S
M +S
L X L L
M
+Y L X

-X
Y
L L L L
M -d[ML 3X]/dt = (k s + ky [Y]) [ML 3X] M
L X L S
+Y

Y
L L
-X M
L S
L L
M -S
L Y
THE trans EFFECT

SIGMA-BONDING EFFECTS

Sigma-Bonding Effect. A strong  bond between Pt and T

weakens the Pt-X bond.

H- > PR3 > SCN- ~ CH3- ~ CO ~ CN- > Br- > Cl- > NH3 > OH-
PI-BONDING EFFECTS

If back donation occurs to a ligand, the flow of electron

density from the metal leaves less electron density to be
donated in the opposite direction.

C2H4 ~ CO > CN- > NO2- > SCN- > I- > Br- > Cl- > NH3 > OH-
Overall trans effect:

CO ~ CN- ~ C2H4 > PR3 ~ H- > CH3- ~ SC(NH2)2 > C6H5- >NO2-
~ SCN ~ I- >Br- > Cl- > py , NH3 ~ OH- ~H2O
SAMPLE PROBLEM:

Predict the products of the reactions (there may be one product

when there are conflicting preferences)

[PtCl4-] + NO2- → (a) (a) + NH3 → (b)

[PtCl3NH3]- + O2- → (c) (c) + NO2- → (d)

SAMPLE PROBLEM:

Is it possible to prepare different isomers of Pt(II)

complexes with 4 different ligands?

Predict the products expected if 1 mole of [PtCl4]- is

reacted successively with the following reagents: (the
product of reaction a is used in reaction b)

a)2 moles NH3

b)2 moles py
c)2 moles Cl-
d)1 mole NO2-
 Electron transfer (redox) reactions

-1e (oxidation)

M1(x+)Ln + M2(y+)L’n M1(x +1)+Ln + M2(y-1)+L’n

+1e (reduction)

Very fast reactions (much faster than ligand exchange)

May involve ligand exchange or not

Very important in biological processes (metalloenzymes)

REDOX MECHANISMS:

Inner sphere mechanism:

When two molecules are connected by a common ligand which
the electron is transferred, in which case the reaction is called
bridging or innersphere reaction.

Outer sphere mechanism:

Exchange may occur between two separate coordination sphere
in outersphere reaction.
 Outer sphere mechanism
[Fe(CN)6]4- + [IrCl6]2- [Fe(CN)6]3- + [IrCl6]3-

[Co(NH3)5Cl]2+ + [Ru(NH3)6]2+ [Co(NH3)5Cl]+ + [Ru(NH3)6]3+

Reactions ca. 100 times faster

than ligand exchange A B "solvent cage"
(coordination spheres remain the same)

r = k [A][B]
Ea
Tunneling A + B A' + B'
mechanism
G
 Inner sphere mechanism

[Co(NH3)5Cl)]2+ + [Çr(H2O)6]2+ [Co(NH3)5Cl)]2+:::[Çr(H2O)6]2+

[Co(NH3)5Cl)]2+:::[Çr(H2O)6]2+ [CoIII(NH3)5(-Cl)ÇrII(H2O)6]4+

[CoIII(NH3)5(-Cl)ÇrII(H2O)6]4+ [CoII(NH3)5(-Cl)ÇrIII(H2O)6]4+

[CoII(NH3)5(-Cl)ÇrIII(H2O)6]4+ [CoII(NH3)5(H2O)]2+ + [ÇrIII(H2O)5Cl]2+

[CoII(NH3)5(H2O)]2+ [Ço(H2O)6]2+ + 5NH4+

 Inner sphere mechanism

k1 k3
Ox-X + Red Ox-X-Red Ox(H2O)- + Red-X+
k2 k4

Reactions much faster

than outer sphere electron transfer Ox-X-Red
(bridging ligand often exchanged)
Tunneling
r = k’ [Ox-X][Red] k’ = (k1k3/k2 + k3) through bridge
Ea mechanism
Ox-X + Red
Ox(H2O)- + Red-X +

G