Organometallic Chemistry:

It is Chemistry of organometallic compounds.

Dr. ABHIMANYU K. YADAV

Asst . Professor
Chemistry Department
G. N. Khalsa college
Co-ordination Complexes:

The electronic basis of the color of metal complexes

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 Coordination complex: A structure containing a metal (usually a metal ion) bonded
(coordinated) to a group of surrounding molecules or ions.

Ligand (ligare is Latin, to bind): A ligand is a molecule or ion that is directly bonded to a
metal ion in a coordination complex

A ligand uses a lone pair of electrons (Lewis base) to bond to the metal ion
(Lewis acid)

Coordination sphere: A metal and its surrounding ligands

Note: religare is Latin, to bind tightly

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Complex ions: Three common structural types

Octahedral:
Tetrahedral Square planar
Most important

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 The formation of a coordinate complex is a Lewis acid-base reaction

Lewis base: Coordination complex: Lewis base

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coordinated to a Lewis acid

Coordination complex: Ligand

(electron donor) coordinated to a
metal (electron acceptor)

Lewis acid: Co3+

The number of ligand bonds to the central metal atom is termed the coordination number

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 The basic idea is that the ligand (Lewis base) is providing electron density to the
metal (Lewis acid)

The bond from ligand to metal is covalent (shared pair), but both electrons
come from the ligand (coordinate covanent bond)

In terms of MO theory we visualize the coordination as the transfer of

electrons from the HO of the Lewis base to the LU of the Lewis acid

Co3+

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 Types of Ligands: Monodentate (one tooth) Ligands

Latin: “mono” meaning one and “dens” meaning tooth

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 Types of Ligands: Bidentate (two tooth) Ligands

Bidentate (chelates):

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 Types of Ligands: Ethylenediaminetetraacetate ion (EDTA): a polydentate chelating
ligand

Chelate from
Greek chela, “claw”

EDTA wraps around the metal ion at all 6

coordination sites producing an
exceedingly tight binding to the metal

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 Alfred Werner: the father of the structure of
coordination complexes

The Nobel Prize in Chemistry 1913

"in recognition of his work on the linkage of
atoms in molecules by which he has thrown
new light on earlier investigations and
opened up new fields of research especially
Alfred Werner in inorganic chemistry"
Switzerland
University of Zurich
Zurich, Switzerland
b. 1866
(in Mulhouse, then Germany)
d. 1919

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Hapticity:-
The term hapticity is used to describe how a group of contiguous
atoms of a ligand are coordinated to a central atom. Hapticity of
a ligand is indicated by the Greek character 'eta', η.
ηn: n = the number of contiguous atoms of the ligand that are bound
to the metal.
 The term is usually employed to describe
ligands containing extended pi-systems or
where agostic bonding is not obvious from
the formula.
 Ferrocene: bis(η5-cyclopentadienyl)iron
 Zeise’s salt: K[PtCl3(η2-C2H4)].H2O
 Uranocene:
bis(η8-1,3,5,7-cyclooctatetraene)uranium
 W(CO)3(PPri
3)2(η2-H2)
 IrCl(CO)[P(C6H5)3]2(η2-O2) 16
Hapticity:- No of carbon attached through which
ligand is attached to to metal ion
EAN:- Total no. of electron around metal is known as EAN.
EAN in valence shell :- Total no. of electron around in
outer orbital of metal is known as EAN in valence shell
.
Metal accept electron pair from ligands till it acqires
ns2,(n-1)d10,np6 outer shell configuration.i.e. 18 e- in
valence shell.
e.g. Fe(CO)5
Total no of electron in Fe valence shell =8 e-
electron contributed by 5 CO = 5×2 = 10 e-
total electron =18 e-
Electron count :-

i) Count electron in outer orbital of free

metal. Add or subtract electron according to charge
on metal in complex.
ii) Count the electron contributed by ligands.
iii) CO terminal contributes 2 e- whereas bridging CO
contributes 1 e-.
iv) Each M ─ M bond contributes 1e-.
v) Summation of all step i to iv gives total e- in valence
shell.
Examples:
 TiCl4 3s23p63d24s2
Neutral counting: Ti 4e, Cl 1e; 4+4(1) = 8 valence electrons
Ionic counting: Ti4+ 0e, Cl 2e; 0+4(2) = 8 valence electrons
Conclusion: Having only 8e (vs. 18 possible), we can anticipate that
TiCl4 will be a good Lewis acid. Indeed, it reacts (in some cases
violently) with water, alcohols, ethers, amines.
• Fe(CO)5 3s23p63d64s2
Neutral counting: Fe 8e, CO 2e, 8 + 2(5) = 18 valence electrons
Conclusion: This is a special case, all fragments being neutral.
Since this is an 18-electron complex, Fe(CO)5 is a stable compound.
• Fe(C5H5)2 , FeCp2
N t l ti F 8 CH 5 18 l t
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Neutral counting: Fe 8e, C5H5 5e: 8 + 2(5) = electrons

Ionic counting: Fe2+ 6e, C5H5
 6e: 6 + 2(6) = 18 electrons
Conclusion: Ferrocene is expected to be a stable compound.
NOTE:
i. These examples show the methods of electron counting, they are a
formalism, and don't have anything to do with real life chemical
transformations. Most of the 'fragments' mentioned above do not
exist as such; they cannot be kept in a bottle. these formalisms
are only used to predict stabilities or properties of compounds!

ii. The 18-electron rule is just that - a rule, not a law. Many MT
complexes do not follow this rule, and, furthermore, compounds
which have fewer than 18 valence electrons tend to show
enhanced reactivity. In fact, 18 electrons is often a recipe for
non-reactivity in either a stoichiometric or catalytic sense.

iii. It is especially useful for organometallic complexes of the Cr, Mn,

Fe, and Co triads, and applies to compounds such as ferrocene,
iron pentacarbonyl, chromium carbonyl and nickel carbonyl.
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18 electron Rule:- In a complex metal will accept
electon from ligands to accquire ns2,(n-1)d10,np6 (i.e. 18
electron in valence shell)
Configuraton to give stable complex
16 electron Rule:-
In a complex metal will accept electon from ligands to
accquire ns2,(n-1)d8,np6 (i.e. 16 electron in valence shell)
Configuraton to give stable complex
IMPORTANT TYPES OF REACTIONS
I. Oxidative addition/Reductive elimination
 In oxidative addition, a metal complex with vacant coordination
sites and a relatively low oxidation state is oxidized by the insertion of
the metal into a covalent bond (X－Y).
 Both the formal oxidation state of the metal and the electron count
of the complex increase by two.
 Oxidative additions can occur with the insertion of a metal into
many different covalent bonds, they are most commonly seen with
 P h 3P
H
CHH 2 H CH2
H
P h 3P Rh CH2
Cl Rh CH2
P Ph P h3P
3
P h3P H Rh H
H 2 CC l C H 2 P h3P
Cl