Metal Complexes

d-block Transition metals: relationship between various

oxidation states, electronic configurations, coordination
numbers and resultant geometry of coordination
complexes.

SUBMITTED TO,
Respected, Dr. Sajid Nawaz

SUBMITTED BY:
Zahid Hussain
PhD (Pharmaceutical Chemistry)
Roll No: DPCH02201005
Hafnium Hf

Ground state configuration :

The ground state electronic configuration of hafnium is   [Xe]
4f14 5d2 6s2.

Possible oxidation states:

The usual oxidation state of hafnium is +2 and The possible
oxidation states of Hafnium are 1,2,3,4

Important Compounds of Hafinium :

It forms alloys with iron, niobium, tantalum, titanium, and other transition metals.
The alloy tantalum hafnium carbide (Ta4HfC5), with a melting point of 4,215 °C
(7,619 °F), is one of the most refractory substances known ..
Its forms compounds like Hafnium carbide with carbon .(HfC), one of the most
refactory binary compound .
With oxygen it form Hafnium oxide.(HfO2) It is one of most coomon and satble
product and it is a electrical insulator
It also has Hafnium tetraiodide compound that is quite important in material
science and acts as a catalyst . , Other compounds are Hafnium tetra fluoride ,
Hafnium diboride ( Hf B2), Hafnium disulfide
Coordination number :
Hafnium has coordination numbers 5,6,7,8. With coordination number 6 the
compound that hafnium forms is HfI3.

Geometrical shapes and Hybridization :-

Hafnium itself has a hexagonal structure . The compounds of hafnium show
geometrical shapes like octahedral , tetrahedral , hexagonal .
 For e.g HfI3 has octahedral shape.
 Hfcl 4 has monometric tetrahedral structure .

 Hafnium diboride has hexagonal crystal structure .

 Hybridization of Hafnium :
Hafnium is a transition metal whose d-electrons can be tied into a hybridized
bond with the sp- electrons of carbon. For example The C/C–HfC composite with a
hybrid matrix consisting of carbon and hafnium carbide (HfC) is fabricated by
impregnating a carbon fiber felt with hafnium oxychloride octahydrate
(HfOCl2·8H2O) aqueous solution, which serves as the HfC precursor.

Tantalum Ta

Ground state electronic configuration :

The ground state electronic configuration of Tantalum is
[Xe].4f14.5d3.6s2
Possible oxidation states:
The oxidation state of Tantalum is +5. And the possible oxidation states
are 5, 4, 3, 2, 1, −1, −3 (a mildly acidic oxide).

Important Compounds of Tantalum :

It occurs, with niobium, in the columbite–tantalite series (in
which columbite [FeNb2O6] and tantalite [FeTa2O6] occur in highly variable
ratios) and the pyrochlore–microlite series of minerals.
Other compounds are tantalum pentoxide Ta2O5. It is a inert material with high
refractive index and low absorption which makes it useful for coatings , Tantalum
chloride Tacl5. Tantalum carbide , Tantalite ,

Coordination number :
Its lowest coordination number 6 that forms a compound with oxygen , fluorine atoms .

Geometrical shapes and Hybridization :-

Tantalum itself has a body centered cubic structure
 While the compounds like Tantalum pentoxide has a monoclinic structure

 Tantalum chloride has a trigonal bypyramidal structure .

 Hybridization of tantalum oxide:-
The reaction of equimolar amounts of 1-n-butyl-3-methylimidazolium chloride
(BMI·Cl) or 1-n-decyl-3-methylimidazolium chloride (DMI·Cl) with TaCl5 affords
imidazolium tantalate ionic liquids (ILs) BMI·TaCl61 and DMI·TaCl62. The
hydrolysis of ILs 1 and 2 yields hybrid-like tantalum oxide nanoparticles (NPs) with
size distribution dependent on the nature of the IL used (3.8–22 nm from IL 1 and
1.5–6 nm from 2). A significant aggregation/agglomeration of the particles was
observed after the removal of the IL content of the hybrid material by calcination,
forming predominantly large particles (mainly bulk tantalum oxides). These new
hybrid-like Ta2O5/IL NPs are highly active photocatalyst nanomaterials for
hydrogen production by reforming of ethanol at ambient temperature. Hydrogen
evolution rates up to 7.2 mmol H2 g−1 h−1 and high apparent quantum yields up
to 17% were measured. The hybrid-like Ta2O5/IL NPs sputtered-decorated with
ultra-small Pt NPs (1.0 ± 0.3 nm) as co-catalysts reached activities leading to even
higher hydrogen production (9.2 H2 mmol g−1 h−1; apparent quantum yield of
22%). The calcined materials (with or without Pt NPs) showed much lower
photocatalytic activity under the same reaction conditions (up to 2.8 mmol g−1 of
H2). The remarkable activity of the hybrid-like Ta2O5/IL NPs may be related to the
presence of the remaining IL that provides hydrophilic regions, facilitating the
approach of polar molecules (water and alcohol) to the semiconductor active
photocatalytic sites.

Tungsten W
Ground state electronic configuration :
The ground state electronic configuration is[Xe]6s 4f 5d
2 14 4

Possible oxidation states:

The common oxidation state is +6 . And the possible oxidation states are 6, 5,
4, 3, 2, 1, 0, −1, −2, −4 (a mildly acidic oxide)

Important Compounds of Tungsten:

The most important tungsten compound is tungsten carbide (WC), which is noted
for its hardness (9.5 on the Mohs scale, where the maximum, diamond, is 10). It is
used alone or in combination with other metals to impart wear-resistance to cast
iron and the cutting edges of saws and drills.
Tungsten also forms hard, refractory, and chemically inert
interstitial compounds with boron, nitrogen, and silicon upon direct reaction with
those elements at high temperatures.
With oxygen it form tungsten oxide WO3 , which is a strong oxidative agent and is
also used for x-ray screen phosphors .With carbon it forms tungsten carbide WC.
With sodium it forms Sodium tungstate . Na2WO4 which is used as catalyst
for epoxidation of alkenes .
 Coordination number :
Normally the maximal coordination number is 9, but in combination with peroxo
ions or a-bound aromatic ring systems it may attain 13.
Examples of coordination number 5 is a compound Trigonal bipyramid structure
i.e [W(CO)52-].
Coordination number 6 compoumd is [W2CO)1012-].

Geometrical shapes and Hybridization :-

Tungsten itself has a body centered cubic structure .
 However the compounds Like tungsten trioxide has a temperature
dependant structure that is tetragonal at temperatures above
740 °C, orthorhombic from 330 to 740 °C, monoclinic from 17 to
330 °C, triclinic from -50 to 17 °C, and monoclinic again at temperatures
below -50 °C

.
 Sodium tungstate has orthorhombic structure

Hybridization of Tungsten :-
Tungsten oxide is done in the presence of a constant amount of deferoxamine,
the particle morphology drastically changes with temperature, ranging from
wormlike organic−inorganic hybrid nanostructures to single-crystalline tungsten
oxide nanowires, highlighting the role of the bioligand in controlling the crystal
growth and assembly behavior. The nanowires have a uniform diameter of about
1.3 nm, an aspect ratio of more than 500, and the structural flexibility of tungsten
oxide. The presented process is based on the combination of biomimetic
construction principles with nonaqueous sol−gel chemistry, thus combining the
advantages of both tools, excellent control over particle morphology and high
crystallinity at low temperature.
 Rhenium Re

Ground state configuration :

The ground state electronic configuration is [Xe]4f  5d  6s
14 5 2.

Possible oxidation states:

The possible oxidation states are 7, 6, 5, 4, 3, 2, 1, 0, −1, −3 (a mildly acidic
oxide)
Important Compounds of Rhenium :
Perrhenic acid (HReO4) and its anhydride, the heptoxide, and the perrhenates are
common stable compounds in which rhenium is in the +7 state.  reactions of the
analogous [Re(R)(CO)5] compounds with phosphines give only the phosphine-
substituted alkyl species; in other words,
The rhenium compounds undergo CO substitution as opposed to alkyl migration.
For example, the reaction of the butanediyl compound [(CO)5Re(CH2)4Re(CO)5]
with tertiary phosphines gives the binuclear phosphine-substituted alkyl
compounds

Coordination number :
It usually has coordination number 4,5,6 . The compound with coordination 4 is
[Re(CO)4]and with coordination number 5 is [Re2Cl8] and with coordination
number 6 is [ReI5]2-

Geometrical shapes and Hybridization :-

Rhenium itself has hexagonal structure
 [Re(CO)4] has tetrahedral structure and [Re2Cl8] is square pyramidal
and[ReI5]2 has octahedral structure .

Hybridization of Rhenium :-
Two novel organic compounds incorporating 8-hydroxyquinoline moiety, namely
2-[2-(2,3-dichlorophenyl)vinyl]quinoline-8-ol (HL1) and 2-[2-(3,5-
dimethoxyphenyl)vinyl]quinoline-8-ol (HL2), have been synthesized and their
interaction with [ReO2(py)(4)]Cl has been examined. The complexes [ReOCl(L-1)
(2)] (1) and [ReOCl(L-2)(2)] (2) have been characterized spectroscopically and
structurally. The experimental studies on the Re(V) complexes have been
accompanied computationally by the density functional theory (DFT) and time-
dependent DFT calculations. Additional information about binding between the
rhenium atom and oxo ligand in the complexes 1 and 2 has been obtained by NBO
analysis.
The occupancies and hybridization of the calculated natural bond orbitals
(NBOs) between the rhenium and the oxo ligands for 1 and 2
 Osmium Os

Ground state configuration :

The ground state electronic configuration is [Xe ]4f  5d  6s
14 6 2

Possible oxidation states:

The oxidation states are +4, +3 and the possible oxidation states are 8, 7, 6, 5, 4, 3,
2, 1, 0, −1, −2, −4 (a mildly acidic oxide)

Important Compounds of Osmium :

Though rare, osmium is found in native alloys with other platinum metals: in
siserskite (up to 80 percent), in iridosmine, in aurosmiridium (25 percent), Of the
platinum metals, osmium is the most rapidly attacked by air. The powdered
metal, even at room temperature, exudes the characteristic odour of the
poisonous, volatile tetroxide, OsO4. Because solutions of OsO4 are reduced to the
black dioxide, OsO2, by some biological materials, it is sometimes used to stain
tissues for microscopic examinations.
Osmium is, with ruthenium, the most noble of the platinum metals, and cold and
hot acids are without effect on them. It can be dissolved by fused alkalies,
especially if an oxidizing agent such as sodium chlorate is present. Osmium will
react at 200° C with air or oxygen to form OsO4.
Osmium also forms Osmium chloride OsCl4. With borides it forms osmium borides
OsB, Os B . With fluorine it forms Osmium hexafluoride, also osmium(VI) fluoride,
2 3

(OsF6) is a compound of osmium and fluorine, and one of the seventeen known

binary hexafluorides.

Coordination number :
Osmium usually has a coordination number 6 For e.g with 6 coordination
number it forms a compound [Os(NH4)6+].

Geometrical shapes and Hybridization :-

Osmium itself has a hexagonal structure
 And compounds like osmium borides areOsB, Os2B3  have hexagonal
structure

 [Os(NH4)6+]. Compound has a octahedral structure

Hybridization of osmium :
The oxidation state of osmium in this compound is +8. Hence it's d-orbitals are
emptied in making the bonds to the oxygen atoms (oxygen is more
electronegative and "hogs" the electrons from osmiums d-orbitals to form
resonance stabilized double bonds). With the d-orbitals unoccupied, osmium can
assume a geometry characteristic of a hybridization between its filled s and p
orbitals.

This isn't the only oxide that forms an sp3 configuration with metals even though
the metal has d-orbitals. The structures for permanganate ion (MnO4-, with Mn at
+7), manganate ion ( MnO42-, with Mn at +6), and Cromate ion (CrO42-, with Cr
at +6) give the same geometry, and if you notice these metals are a few rows up
the periodic table and appear just to the left of osmium's group.

Iridium Ir
Ground state configuration :
Its ground state elecetronic configuration is Xe]4f 5d14 9

Possible oxidation states:

The possible oxidation states are +1, +3, +4

Important Compounds of Iridium:

 Iridium is chiefly used in the form of platinum alloys. Platinum-iridium alloys (5
to 10 percent iridium) are readily workable metals that are much harder and
stiffer and more resistant to chemical attack than the soft pure platinum. Such
alloys are used for jewelry, pen points, surgical pins and pivots, and electrical
contacts and sparking points. 
Though rare, iridium does occur in natural alloys with other noble metals:
in iridosmine up to 77 percent iridium, in platiniridium up to 77 percent,
in aurosmiridium 52 percent, and in native  up to 7.5 percent. Iridium forms
Iridium chloride IrCl3. Hydrated iridium(III) chloride is used in the laboratory for
the preparation of other iridium compounds such as Vaska's complex, trans-
[IrCl(CO)(PPh3)2].
Ammonium hexachloroiridate(IV) is the inorganic compound with the formula
(NH4)2[IrCl6]. 

Coordination number :
Iridium has coordination number 4 and the compound it forms with this
coordination is [Ir(CO)Cl(PPh3)2.and with coordination number 6 it forms IrF6.

Geometrical shapes and Hybridization :-

Iridum itself has a face centered cubic structure .
 IrCl3 has monoclinic structure
  In Ammonium hexachloroiridate The [IrCl6]2− centers adopt octahedral

molecular geometry.

Hybridization of iridium : -
Hybridization properties of iridium(III) polypyridyl complex-conjugated
oligonucleotide were studied An Ir(III) polypyridyl complex-conjugated 14-mer
oligonucleotide (IrIII-DNA) was synthesized and its hybridization properties with
single-stranded DNA (ssDNA) and double-stranded DNA (dsDNA) were evaluated
by UV-melting experiments. The stabilities of the duplexes of IrIII-DNA with 14-,
20-, and 26-mer ssDNAs were higher than those of the unconjugated
oligonucleotides. The triplex of IrIII-DNA with 14-mer dsDNA was also stabilized.
However, the triplexes of IrIII-DNA with 20- and 26-mer dsDNAs, flanked by 3 and
6 base pairs at the both ends of 14-mer dsDNA target, were destabilized. This is
presumably because of steric repulsion between the Ir(III) complex and the
protruding 3- and 6-mer dsDNA moieties which are inflexible compared to ssDNA.
 Platinum Pt

Ground state configuration :

The ground state elecetronic configuration is [Xe]4f  5d  6s
14 9

Possible oxidation states:

The oxidation states are +4, +2, and the possible oxidation states are 6, 5,
4, 3, 2, 1, −1, −2, −3 (a mildly basic oxide)
Important Compounds of Platinium :
Platinum also combines with a number of nonmetallic elements on heating, such
as phosphorus, arsenic, antimony, silicon, sulfur, and selenium. Platinum occurs
combined with arsenic as sperrylite (PtAs2) in the copper–nickel-mining district
near Sudbury,. IT is on eof the native elements ,  platinum-iridium is used for
surgical pins.
It forms Cisplatin with Cl and ammonia and it is a major chemotherapeutic drug .
Triplatin tetranitrate (rINN; also known as BBR3464) is a platinum-based cytotoxic
drug that underwent clinical trials for the treatment of human cancer.

Coordination number :
Platinum commonly has coordination number 6 and compound it forms with
this number is PtF6.

Geometrical shapes and Hybridization :-

Platinum itself has a face centered cubic structure .
 Its compounds like Cisplatin is the square planar coordination complex cis-
[Pt(NH3)2Cl2]

 PtF6. has a octahedral structure .

Hybridization of platinum :-
The Hybridisation of [PtCl4]2- as   and it has structure of square planar 
Electrons in valence shell of Pt i.e 4d is eight and 5s is 2. Here valency of Pt is
+2.So electrons of 5s becomes zero.
For 4d and 5d series all ligands act as strong ligands hence pairing occur. The 2
unpaired electron in 4d of Pt get paired and hence there is one vacant orbital.
Hence one orbital of 4d, 5s and two orbitals of 5p participates in hybridization,
resulting in dsp2 type of hybridization and square planar geometry.

Gold Au

Ground state configuration :

The ground state electronic configuration is [Xe]4f 5d 6s

14 10
Possible oxidation states:
The normal oxidation states are +1, +3,and the possible oxidation states
are −3, −2, −1, 0,[2] +1, +2, +3, +5 (an amphoteric oxide)

Important Compounds of Au Gold :

Among the relatively few gold compounds of practical importance are gold(I)
chloride, AuCl; gold(III) chloride, AuCl3; and chlorauric acid, HAuCl4. In the
first compound, gold is in the +1 oxidation state, and in the latter two, the +3
state. All three compounds are involved in the electrolytic refining of gold. 
Potassium cyanoaurate, K[Au(CN)2], is the basis for most gold-plating baths (the
solution employed when gold is plated). Several organic compounds of gold have
industrial applications. For example, gold mercaptides, which are obtained from
sulfurized terpenes, are dissolved in certain organic solutions and used for
decorating china and glass articles
Gold chloride AuCl3 has attracted the interest of organic chemists as a mild acid
catalyst for a variety of reactions.
Auranofin is a gold salt that is capable of eliciting pharmacologic actions that
suppress inflammation and stimulate cell-mediated immunity.

Coordination number :
The majority have coordination number 2 with a linear geometry for example
gold carbide Au2C2, 

Geometrical shapes and Hybridization :-

It itself has a face centered cubic structure .
 Its compound like gold(III) chloride, each gold center is square planar.
  Auranofin structure is

Hybridization of Gold:
. For gold, the 5d orbitals are core-like and only hybridize slightly with the 6s,
where the 6p valence orbitals are too highlying to contribute significantly to the
bonding. The geometries have been classified as (i) spherical polyhedral clusters
characterized by a total of 12n þ 8 valence electrons (n is the number of
peripheral gold atoms); and (ii) toroidal or elliptical polyhedral clusters
characterized by a total of 12n þ 6 valence electrons
Mercury Hg

Ground state configuration :

The ground state elecetronic configuration is (Xe)4f 5d 6s
 14 10 2

Possible oxidation states:

The possible oxidation states are +1 or +2 

Important Compounds of Hg :
Hg2Cl2 (commonly known as calomel), is probably the most important univalent
compound. It is used in antiseptic salves. Mercury(II) chloride, HgCl2 (also
called bichloride of mercury or corrosive sublimate), is perhaps the commonest
bivalent compound. Although extremely toxic, this odourless, colourless
substance has a wide variety of applications. In agriculture it is used as a
fungicide; in medicine it is sometimes employed as a topical antiseptic in
concentrations of one part per 2,000 parts of water; and in the chemical
industry it serves as a catalyst in the manufacture of vinyl chloride and as a
starting material in the production of other mercury compounds. Mercury(II)
oxide, HgO, provides elemental mercury for the preparation of various organic
mercury compounds and certain inorganic mercury salts. This red or
yellow crystalline solid is also used as an electrode (mixed with graphite) in zinc-
mercuric oxide electric cells and in mercury batteries.
Mercury(II) sulfide, HgS, is a black or red crystalline solid used chiefly as a pigment
in paints, rubber, and plastics.

Coordination number :
The range of coordination number varies from 2 to 10. The most common
coordination number is four for example in K2[HgI4]. The coordination number is
4.

Geometrical shapes and Hybridization :-

Mercury itself has a rhombohedral structure .
 Its compounds like HgCl2 has orthogonal structure .

Hybridization of mercury :
For HgCl2 you will first have to write the electronic configuration for the central
atom and the others .The Atomic number of Hg is 80 so ,electronic configuration
for Hg is [Xe] 4f14 5d10 6s2 know it is so easy there is no lone paires with Hg and
the number of bonding paire are two hence the only posdible hybridization is SP
hybridization and the structure is Linear hence only two hybrid one S and one P .
Cl-Hg-Cl