Module-2: Metal Complexes and Organometallics 6hrs

• Inorganic complexes - Structure, bonding and applications.

Zeise's salt- first organometallic
compounds . The metal is coordinated to
the C=C double bond. has low
cytotoxicity against cancer cells
• Organometallics – introduction, stability,
• Structure and applications of metal carbonyls, ferrocene and
Grignard reagent.

• Metals in biology - haemoglobin and chlorophyll - structure and

property). heme

Dr. A. A. NAPOLEON, M. Pharm., PhD

Professor
Dept. of Chemistry, SAS
VIT University, Vellore – 14.
Cabin: TT-212, Mobile No: 9842626161 1
 Contents…..(6 hours)

Inorganic complexes - structure, bonding and applications

Organometallics – introduction, stability, structure and

applications of metal carbonyls and ferrocene

Metals in biology: haemoglobin and chlorophyll- structure and

property

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 Module-2: Metal Complexes and Organometallics 6hrs
a. Inorganic complexes - Structure, bonding and applications.
Double Salts and Coordination Compounds,
Ligands- Metal Ligand bonds- Unidentate, Bidentate, Polydentate with examples
Chelating Agents: Key difference between complexing agent and chelating agent:
Werner Coordination Theory: 2 types of valency- primary and secondary
Formation of complex compounds, Important postulates of Werner’s theory
Structure of CoCl3.6NH3 Complex, [Co(NH3)6]3Cl-
Lewis Acid Base Theory - Gilbert N. Lewis, 1920s
Sidgwick’s Effective Atomic Number (EAN) rule
Valence Bond Theory (Linus Pauling, 1931)

Bonding in Coordination Compounds: Crystal field theory (CFT), Ligand Field theory
b. Organometallics – introduction, stability, structure and applications of metal carbonyls,
ferrocene and Grignard reagent
c. Metals in biology - haemoglobin and chlorophyll - structure and property).
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 Inorganic Complexes
• Inorganic/coordination complex is a molecule containing one or multiple metal
centers that is bound to ligands (atoms, ions, or molecules that donate electrons
to the metal).

• These complexes can be neutral or charged. The examples are:

Neutral Complexes: [CoCl3(NH3)3], K4[Fe(CN)6], etc.

Cationic Complex : [CO(NH3)6]3+ and Anionic Complex : [CoCl4(NH3)2]−

Selected examples of metal complexes with names:

[Co(NH3)5Cl]Cl2 --- Chloropentaamminecobalt(III) chloride
[Cr(H2O)4Cl2]Cl --- Dichlorotetraaquochromium(III) chloride
K[PtCl3(NH3)] --- Potassiumtrichloroammineplatinate(II)
[PtCl2(NH3)2] --- Dichlorodiammineplatinum(II) 4

[Co(en)3Cl3] --- tris(ethylenediamine)cobalt(III)chloride

[Ni(PF3)4] --- tetrakis(phosphorus(III)fluoride)nickel(0)
 Applications of Coordination Compounds
 Coordination compounds are of great importance.
 Play many important functions in the area of analytical chemistry, metallurgy, biological
systems, industry and medicine.
 Catalysis
 Extraction and Purification of metal ions:
By the formation of cyanide complexes - dicyanoargentite(I) - [Ag(CN)2]– and
dicyanoaurate separated by the addition of zinc for the separation of noble metal
Ag↓
[Ni(CO)4], which is decomposed to yield pure nickel.
Analytical chemistry (development of numerous analytical methods)
 Nickel estimation- DMG (dimethylglyoxime)
 Hardness estimation: EDTA
❖Biological importance: Haemoglobin, the red pigment of blood which acts
as oxygen carrier is a coordination compound of iron.
Vitamin B12, cyanocobalamine, is a coordination compound of cobalt.
Medicinal application: Excess of copper and iron are removed by the chelating ligands
D–penicillamine and desferrioxime B via the formation of coordination compounds.

Industrial application:
 Chelation Therapy: British Anti-Lewisite (BAL),
2,3-dimercaptopropanol. forms stronger complex with arsenic – acts as an antidote.
Inorganic Complexes: Structure, Bonding and Applications
Double Salts: Mixture of two simple salts but with a different crystal
structure from either
Ferric alum [Ferric(III) Ammonium Its a weak Mohr's salt [Ferrous(II) Ammonium
oxidizing agent Sulphate], (NH4)I2FeII(SO4)2.6H2O
Sulphate], NH4IFeIII(SO4)2.12H2O contain 2 diff. cations (Fe2+ and NH4+)
and capable of and is classified as a double
contain 2 diff. cations (Fe3+ and being reduced salt of ferrous sulphate,
NH4+) and is classified as a double to FeSO4 and ammonium sulphate,
salt of ferric sulphate, Fe2(SO4)3 (NH4)2SO4
and ammonium sulphate,
Synthesis: FeSO4 + (NH4)2SO4  (NH4)2Fe(SO4)2
(NH4)2SO4
Synthesis: Fe2(SO4)3 + (NH4)2SO4  2 NH4Fe(SO4)2
Dissociate in water as NH4+, SO42-, Fe3+/Fe2+
Inorganic Complexes: Structure, Bonding and Applications
Double Salts and Coordination Compounds
❖ Double Salt:
Ferric alum (NH4)2SO4.Fe2(SO)4.24H2O
In water: NH4+, SO42-, Fe3+ Co-ordination Compounds

Coordination Compounds Fe(CN)2 + 4KCN

Fe(CN)2.4KCN
3Cl
–

(counterion)
4K+ +
[Fe(CN)6]4-
ligand M
(coordination
sphere)

N forms a coordinate Potassium hexa cyano ferrate

covalent bond to the metal
❖Co-ordination Compounds Differences between double salt and
coordination complex salt
Chemical structures in which a central
metal atom is surrounded by non-metal
atoms or groups of atoms, called ligands.

Fe(CN)2 + 4KCN
Fe(CN)2.4KCN

4K+ +
[Fe(CN)6]4-
 Ligands
▪ Molecule or ion having a lone electron pair that can be used
to form a bond to a metal ion (Lewis base- electron pair which
is not involved in bonding.).
▪ coordinate covalent bond: metal-ligand bond
▪ monodentate : one bond to metal ion
▪ bidentate : two bonds to metal ion
▪ polydentate : more than two bonds to a metal ion possible

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Ligands: Molecule or ion having a lone pair of electron that can be used to form
a bond to a metal ion.
Coordinate covalent bond (metal-ligand bond): Molecule or ion having a
lone electron pair (Lewis base) that can be used to form a bond to a metal
ion ((Lewis acid).
▪ Monodentate : 1 bond to metal ion (Have 1 donor atom)
▪ Bidentate : : 2 bonds to metal ion (Have 2 donor atoms)
▪ Polydentate : >2 bonds to metal ion (Have more than 2 donor atoms)

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 Chelating Agents- (chelants, chelators, or sequestering agents. ...
Chelating agents are chemical compounds that react with metal ions to form a
stable, water-soluble complex.
Chelating agents are compounds that form complexes with metal ion.
Chelating agent is a chemical that catches' a metal ion (charged particle)
They are also known as chelants, chelators, or sequestering agents. ...

Specific chelating agents bind iron, lead, or copper in the blood and can be used to
treat excessively high levels of these metals.

• A chelate is a cyclic compound which has a central metal atom bonded to at least
two other atoms.
• Chelators selectively promote excretion of toxic metals from our body as
the chelator-metal complexes.

Desferoxamine, Deferasirox and deferiprone

are highly specific for iron and have little or
no effect on levels of copper, lead, calcium,
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magnesium
 Complexing agent and Chelating Agents
Complexing agent is an ion, molecule or a functional group that can
bind with a metal ion through one or several atoms to form a large
complex.

Chelating agent is a compound that can bind with a metal ion to

produce a chelate through several atoms in the same molecule.

Unlike ligands, chelating agents are multi-dentate ligands, and there are no mono-
dentate chelating agents.

Chelating agent : A chemical compound

that binds tightly to metal ions. In
medicine, chelating agents are used to heme
remove toxic metals from the body.
Chelating Agents

• Bind to metal ions removing them • Important biomolecules like

from solution. heme and chlorophyll are
porphyrins
• Phosphates are used to tie up Ca2+
and Mg2+ in hard water to prevent
them from interfering with
detergents.
 Werner Coordination Theory
Alfred Werner - Swiss chemist defined the basics of
coordination chemistry, work for which he was
Werner's theory states that- awarded the Nobel Prize in chemistry in 1913.
1. Metals possess two types of valencies called primary / ionizable and
secondary / non - ionizable valency.
2. Every metal atom has a tendency to satisfy both its primary and secondary valencies.

3. The ligands satisfying secondary valencies are always directed towards fixed positions in
space thereby giving a definite geometry to the complex but primary valencies are non - directional.

4. Primary valency relates to the oxidation state & Secondary valency relates to the coordinate number.
.

Coordination number is the term proposed by

Werner
to denote the total number of bonds from the
ligands to the central metal atom.

This numbers generally range between 2 and 12,

with 4 (tetracoordinate) and
Dotted line represents the primary valency.
Normal line represents the secondary valency.

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 Werner Coordination Theory

3 No
III IV

Alfred Werner defined the basics of coordination chemistry, work for which he was
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awarded the Nobel Prize in chemistry in 1913.
Werner Coordination Theory on the formation of complex compounds
Important postulates of Werner’s theory:
• Central metal atom(s) in coordination compounds show 2 types of valency (primary and
secondary).
• Primary valency relates to the oxidation state & Secondary valency relates to the
coordinate number.
• Number of secondary valences is fixed for every metal atom. i.e. the coordination number
is fixed.
• Metal atom works towards satisfying both its primary and secondary valencies.
• A negative ion satisfies the primary valency.
• On the other hand, a negative ion or neutral molecules satisfy secondary valencies.
• Primary valency is non-directional. On the other hand, Secondary valencies point towards
a fixed position in space. This is the reason behind the definite geometry of the
coordinate compound. Therefore, the secondary valency determines
the stereochemistry of the complex ion.
For ex.
A metal ion having 6 secondary valencies
arrange in octahedral geometry around
the central metal ion.

If the metal ion has 4 secondary valencies, these arrange in either tetrahedral or square-
planar arrangement around the central metal ion.
Werner Coordination Theory
 Lewis Acid Base Theory- Gilbert N. Lewis, 1920s
❖ Formation of Metal Complexes or coordinate covalent bonds in metal-ligand
complexes is described as acid-base reaction according to Lewis theory.

❖ Lewis Acid/Base reactions:

❖ Acid: Electron pair acceptor ;
❖ Base: Electron pair donor

Ligands are Lewis bases ;

Metals are Lewis acid

Sidgwick’s Effective atomic number (EAN) rule

Sidgwick’s Effective atomic number (EAN) rule is based on the octet theory of Lewis and

This is the first attempt to account for the bonding in complexes.

 Sidgwick’s Effective atomic number (EAN) rule: 18-electron rule
18 Valence Electron Rule or The Inert Gas Rule or The Effective Atomic Number (EAN) Rule:

Effective atomic number (EAN), number that represents the total number of electrons
surrounding the nucleus of a metal atom in a metal complex. ...

• Effective atomic number (EAN): It is composed of the metal atom’s electrons and the
bonding electrons from the surrounding electron-donating atoms and molecules.

The EAN rule is often referred to as the “18-electron rule” since, if one counts
only valence electrons (6 for Co3+ and 2 × 6 = 12 for 6 NH3), the total number is 18.

The 18-valence electron (VE) rule states that thermodynamically stable transition metal
compounds contain 18 valence electrons comprising of the metal d electrons plus the
electrons supplied by the metal bound ligands.

Metal atom tends to surround itself with sufficient ligands that the resulting EAN is
numerically equal to the atomic number of the noble-gas element found in the same period
in which the metal is situated.

Why is the 18-electron rule important? Or the Applications of 18 Electron Rule?

Predicts the stability of various organometallic compounds.
Predicts the reactivity of transition elements.
Used to predict & refine the formulas of various complex compounds &
organometallic compounds. 19
Used to predict the existence of metal-metal bonds in complexes..
 Sidgwick’s Effective atomic number (EAN) rule: 18-electron rule
• Sidgwick’s Effective atomic number (EAN) rule is based on the octet theory of Lewis and this
is the first attempt to account for the bonding in complexes.

• Effective atomic number (EAN): It is composed of the metal atom’s electrons and the
bonding electrons from the surrounding electron-donating atoms and molecules.

• Metal atom tends to surround itself with sufficient ligands that the resulting EAN is
numerically equal to the atomic number of the noble-gas element found in the same period
in which the metal is situated
•

• Ex: EAN of Cobalt atom (A.N. 27, [Ar] 3d7 4s2) in the complex [Co(NH3)6]3+ = 36 (Krypton),
i.e. the number of electrons in Co3+ ion (24) + number of bonding electrons from 6
surrounding NH3 molecules (2 e- × 6 NH3 = 12) => 36 (Kr).

• EAN rule is often referred to as the “18-electron rule” since, if one counts only valence
electrons of Co3+ (6) + (2 e- × 6 NH3) = 18.

• By using this rule, it is possible to predict the number of ligands in these types
of compounds and also the products of their reactions.
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 Effective atomic number (EAN)- Calculation

Effective atomic number (EAN) in a complex is defined as the total number of

electrons Present around the central metal ion.

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Effective atomic number (EAN) rule: 18-electron rule- Practice questions
• EAN of Cobalt atom (A.N. 27, [Ar] 3d7 4s2) in the complex [Co(NH3)6]3+ = 36 (Krypton), i.e.
• The number of electrons in Co3+ ion (24) + number of bonding electrons from 6 surrounding NH3
molecules
• (2 e- × 6 NH3 = 12) => 36 (Kr).

Kr

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 Valence bond theory: Linus Pauling 1931 & John C. Slater
The valence bond (VB) theory, proposed by American scientists Linus Pauling and
John C. Slater, bonding is accounted for in terms of hybridized orbitals of the metal ion,
which is assumed to possess a particular number of vacant orbitals available for coordinate
bonding that equals its coordination number.
The basis of VB theory is the Lewis concept of the electron-pair bond.

What is the valence bond theory? Theory which describes chemical bonding.
VBT states that the overlap of incompletely filled atomic orbitals leads to the formation of
a chemical bond between two atoms.
The unpaired electrons are shared and a hybrid orbital is formed.

What is valence bond theory explain?

In valence bond theory, the atomic orbitals of individual atoms are combined to form
chemical bonds.
The other major theory of chemical bonding is molecular orbital theory or MO theory.

Valence bond theory is used to explain how covalent chemical bonds form between several
molecules.
VB theory focus on atomic orbitals of the dissociated atoms combining to give
individual chemical bonds when a molecule is formed.
It predicts that metal complex bonding arises from the overlap of vacant 23metal
and filled ligand orbitals.
 Valence Bond Theory (Linus Pauling & John C. Slater 1931)
Valence bond theory predicts that the bonding in a metal complex arises from
overlap of filled ligand orbitals and vacant metal orbitals.

Coordination number is the number of

atoms, ions, or molecules that a central
atom or ion carries in a complex or
coordination compound.

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 Periodic Table

Transition metals: Chemically they show variable valency and

Strong tendency to form coordination compounds, and
Many of their compounds are coloured. e.g.
iron, manganese, chromium, and copper etc

Metallic elements occupying a central block (Groups 4–12) in the periodic table,
 Valence Bond Theory (Linus Pauling, 1931)
Valence bond theory predicts that the bonding in a metal complex arises from overlap of
filled ligand orbitals and vacant metal orbitals.

Practice for [Co(CN)6]3- = Hybridization, Geometry & Magnetic property???

Spectrochemical Series
▪ For a given ligand, the color depends on the oxidation
state of the metal ion.

I- < Cl- < F- < OH- < H2O < SCN- < NH3 < en < NO2- < CN- < CO

WEAKER FIELD STRONGER FIELD

❖ Complexes of cobalt (III)
show the shift in color due
SMALLER Δ LARGER Δ
to the ligand.
❖ (a) CN–, (b) NO2–, (c) phen,
LONGER λ SHORTER λ (d) en, (e) NH3, (f) gly, (g)
H2O, (h) ox2–, (i) CO3 2–

•For a given metal ion, the color depends on the ligand.

Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
 [CuCl4]2- Tetrahedral Geometry
[CuCl4]2- • Tetrahedral copper complex SP3
Cu: Ground state : 29: [Ar] 3d104s1

Hybridisation: SP3 (Outer Orbital Complex)

Geometry; Tetrahedral
Magnetic Nature: paramagnetic -Attracted by magnets –

(N= 1 unpaired electrons- High spin complexes

= 𝟏. 𝟕𝟑𝟐 B.M
Octahedral Geometry- Paramanetic
Square Planar Geometry [Ni(CN)4]2-

Ni: Ground state : 28:[Ar] 3d8 4s2

• Square planar nickel complex [Ni(CN)4]2- Square planar

3d 4s 4p
Ni; (3d84s2)

[Ar] 3d8 Ni2+

[Ni(CN)4]2-
Strong Field Ligands: CN; Pairs up;

• All paired electrons – Diamagnetic - weakly repelled by magnets –

• No Unpaired electrons, hence Low spin complexes
 Valence Bond Theory (Linus Pauling, 1931)
Valence bond theory predicts that the bonding in a metal complex arises from overlap of filled
ligand orbitals and vacant metal orbitals.

Cobalt Ground state; 27; [Ar] 3d74s2

Fe: 26: Ground state; Ar: 3d64s2

 Valence Bond Theory: Limitations

• it does not give explain magnetic properties.

• It does not explain the color indicated by coordination

compounds.
• It does not give an explanation of the
thermodynamic/kinetic stabilities of coordination
complexes.

• It does not differentiate between weak/strong ligands.

Deduce the structure of metal complexes or ions through VBT
Practice questions: Valence Bond Theory