Introduction

Chlorophyll, haemoglobin and vitamin B12 are

coordination compounds of magnesium, iron and
cobalt, respectively.
 Postulates of Werner’s Theory
❑ In coordination compounds metals show two types of linkages
(valences)-primary and secondary.
❑ The primary valences are normally ionisable and are satisfied by
negative ions.
❑ The secondary valences are non-ionisable. These are satisfied by
neutral molecules or negative ions.
❑ The secondary valence is equal to the coordination number and is
fixed for a metal.
❑ The ions/groups bound by the secondary linkages to the metal
have characteristic spatial arrangements (octahedral, tetrahedral
and square planar) corresponding to different coordination
numbers.
❑ [Co(NH3)6] 3+, and [CoCl2(NH3)4] + are octahedral entities, while
[Ni(CO)4] and [PtCl4] 2– are tetrahedral and square planar,
respectively.
Difference between a double salt and a complex

❑ Double salts dissociate into simple ions completely

when dissolved in water.
✓Examples: carnallite KCl.MgCl2.6H2O
✓Mohr’s salt FeSO4.(NH4)2SO4.6H2O
✓Potash alum KAl(SO4)2.12H2O

❑ Complex ions do not dissociate into constituents

ions Fe2+ and CN– ions.
✓Examples: [Fe(CN)6] 4– of K4Fe(CN)6, do not dissociate
into Fe2+ and CN– ions.
 Limitations of Werner’s theory
It could not explain the following:
❑ Only certain elements are capable of forming
coordination compounds.
❑ Bonds in coordination compounds have
directional properties.
❑ Coordination Compounds have characteristic
magnetic and optical properties.
Scientific vocabulary
Coordination entity
• A coordination entity constitutes a central metal atom or ion bonded to a
fixed number of ions or molecules.
• For example, [CoCl3(NH3)3] is a coordination entity in which the cobalt ion is
surrounded by three ammonia molecules and three chloride ions.

Central atom/ion
• In a coordination entity, the atom/ion to which a fixed number of
ions/groups are bound in a definite geometrical arrangement around it, is
called the central atom or ion.
• For example, the central atom/ion in the coordination entities: [NiCl2(H2O)4],
[CoCl(NH3)5] 2+ and [Fe(CN)6] 3– are Ni2+, Co3+ and Fe3+, respectively.
• These central atoms/ions are also referred to as Lewis acids.

Ligands
• The ions or molecules bound to the central atom/ion in the coordination
entity are called ligands.
• These may be simple ions such as Cl–, small molecules such as H2O or NH3,
larger molecules such as H2NCH2CH2NH2 or N(CH2CH2NH2)3 or even
macromolecules, such as proteins.
 Classification of ligands
Unidentate ligand
When a ligand is bound to a metal ion through a single donor atom,
as with Cl– , H2O or NH3, the ligand is said to be unidentate.

Didentate ligand
When a ligand can bind through two donor atoms as in
H2NCH2CH2NH2 (ethane-1,2-diamine) or C2O4 2– (oxalate), the
ligand is said to be didentate.

Polydentate ligand
When several donor atoms are present in a single ligand as in
N(CH2CH2NH2)3, the ligand is said to be polydentate.
Ethylenediaminetetraacetate ion (EDTA4–) is a hexadentate ligand. It
can bind through two nitrogen and four oxygen atoms to a central
metal ion.
Chelate ligand, chelate complexes and
denticity

• When a di- or polydentate ligand uses its two or

more donor atoms to bind a single metal ion, it is
said to be a chelate ligand.

• The number of such ligating groups is called the

denticity of the ligand.

• Such complexes, called chelate complexes tend to

be more stable than similar complexes containing
unidentate ligands.
 Ambidentate ligands

Ambidentate ligand
• Ligand which can ligate through two different atoms is called
ambidentate ligand.
• Examples of such ligands are the NO2 – and SCN– ions.
• NO2 – ion can coordinate either through nitrogen or through
oxygen to a central metal atom/ion.
• Similarly, SCN– ion can coordinate through the sulphur or nitrogen
atom.
Coordination number
The coordination number (CN) of a metal ion in a complex can be
defined as the number of ligand donor atoms to which the metal is
directly bonded.
For example, in the complex ions, [PtCl6] 2– and [Ni(NH3)4]2+, the
coordination number of Pt and Ni are 6 and 4 respectively.

It is important to note here that coordination number of the central atom/ion is

determined only by the number of sigma bonds formed by the ligand with the
central atom/ion. Pi bonds, if formed between the ligand and the central atom/ion,
are not counted for this purpose.

Coordination sphere
The central atom/ion and the ligands attached to it are enclosed in
square bracket and is collectively termed as the coordination sphere.
The ionisable groups are written outside the bracket and are called
counter ions. For example, in the complex K4[Fe(CN)6], the
coordination sphere is [Fe(CN)6]4– and the counter ion is K+.
 Coordination polyhedron
The spatial arrangement of the ligand atoms which are
directly attached to the central atom/ion defines a
coordination polyhedron about the central atom.
The most common coordination polyhedra are octahedral,
square planar and tetrahedral.
Oxidation number of central atom
• The oxidation number of the central atom in a complex is
defined as the charge it would carry if all the ligands are
removed along with the electron pairs that are shared with
the central atom.
• For example, oxidation number of copper in [Cu(CN)4] 3– is +1
and it is written as Cu(I).

Homoleptic and heteroleptic complexes

• Complexes in which a metal is bound to only one kind of
donor groups, e.g., [Co(NH3)6]3+, are known as homoleptic.
• Complexes in which a metal is bound to more than one kind
of donor groups, e.g., [Co(NH3)4Cl2]+ , are known as
heteroleptic.
Pt Cl
Assessment 1
Answers to assessment 1
Answers to assessment 2
Assessment 2
Isomerism in coordination compounds
Isomerism in coordination compounds
Isomerism in coordination compounds
Bonding in Coordination Compounds
Werner’s theory could not answer basic questions like:
▪ Why only certain elements possess the remarkable
property of forming coordination compounds?
▪ Why the bonds in coordination compounds have
directional properties?
▪ Why coordination compounds have characteristic
magnetic and optical properties?

Modern approaches were put forth like:

✓ Valence Bond Theory (VBT)
✓ Crystal Field Theory (CFT)
✓ Ligand Field Theory (LFT)
✓ Molecular Orbital Theory (MOT)
 Valence Bond Theory (VBT)
Postulates

• According to this theory, the metal atom or ion under the influence of
ligands can use its (n-1)d, ns, np or ns, np, nd orbitals for hybridisation
to yield a set of equivalent orbitals of definite geometry.
• These hybridised orbitals are allowed to overlap with ligand orbitals
that can donate electron pairs for bonding.
• It is usually possible to predict the geometry of a complex from the
knowledge of its magnetic behaviour on the basis of the valence
bond theory.
Inner and outer orbital complexes
Bonding in [Ni(CN)4]2-
Bonding in [NiCl4]2-
Bonding in [Ni(CO)4]
 Limitations of Valence Bond Theory
While the VB theory, to a larger extent, explains the formation,
structures and magnetic behaviour of coordination compounds, it
suffers from the following shortcomings:

• It involves a number of assumptions.

• It does not give quantitative interpretation of magnetic data.
• It does not explain the colour exhibited by coordination
compounds.
• It does not give a quantitative interpretation of the
thermodynamic or kinetic stabilities of coordination compounds.
• It does not make exact predictions regarding the tetrahedral and
square planar structures of 4-coordinate complexes.
• It does not distinguish between weak and strong ligands.
 Crystal Field Theory

Postulates
• The crystal field theory (CFT) is an electrostatic model which considers the
metal-ligand bond to be ionic arising purely from electrostatic interactions
between the metal ion and the ligand.
• Ligands are treated as point charges in case of anions or dipoles in case of
neutral molecules.
• The five d orbitals in an isolated gaseous metal atom/ion have same
energy, i.e., they are degenerate.
• This degeneracy is maintained if a spherically symmetrical field of negative
charges surrounds the metal atom/ion.
• However, when this negative field is due to ligands in a complex, it
becomes asymmetrical and the degeneracy of the d orbitals is lifted. It
results in splitting of the d orbitals.
• The pattern of splitting depends upon the nature of the crystal field.
Crystal field splitting ❑ The degeneracy of the d orbitals has
been removed due to ligand electron-
in octahedral metal electron repulsions in the
coordination entities octahedral complex to yield three
orbitals of lower energy, t2g set and
two orbitals of higher energy, eg set.

❑ This splitting of the degenerate levels

due to the presence of ligands in a
definite geometry is termed as
crystal field splitting and the energy
separation is denoted by Δo (the
subscript o is for octahedral).

❑ Thus, the energy of the two eg orbitals

will increase by (3/5) Δo and that of
the three t2g will decrease by (2/5)Δo.

❑ The crystal field splitting, Δo, depends

upon the field produced by the ligand
and charge on the metal ion.
 Spectrochemical series

• Some ligands are able to produce strong fields in which case, the
splitting will be large whereas others produce weak fields and
consequently result in small splitting of d orbitals.
• In general, ligands can be arranged in a series in the order of
increasing field strength as given below: this is known as the
spectrochemical series.
❑ In d1 the single d electron occupies one of the lower energy t2g
orbitals.
❑ In d2 and d3 the d electrons occupy the t2g orbitals singly in
accordance with the Hund’s rule.
❑ In d4 ions, two possible patterns of electron distribution arise:

The two options are:

❑ If Δo < P, the fourth electron enters one of the eg orbitals
giving the configuration t2g3 eg1. Ligands for which Δo < P are
known as weak field ligands and form high spin complexes.

❑ If Δo > P, it becomes more energetically favourable for the

fourth electron to occupy a t2g orbital with configuration t2g4
eg0. Ligands which produce this effect are known as strong
field ligands and form low spin complexes.
Crystal field splitting ❑ In tetrahedral coordination
entity formation, the d orbital
in tetrahedral splitting is inverted and is
coordination entities smaller as compared to the
octahedral field splitting.

❑ For the same metal, the same

ligands and metal-ligand
distances, it can be shown
that Δt = (4/9) Δ0.

❑ Consequently, the orbital

splitting energies are not
sufficiently large for forcing
pairing and, therefore, low
spin configurations are rarely
observed.
 Merits and demerits of CFT
Merits of Crystal Field Theory
✓ The crystal field model is successful in explaining the formation,
structures, colour and magnetic properties of coordination
compounds to a large extent.

Demerits of Crystal Field Theory

✓ Based on assumptions in CFT, the ligands are point charges. This
means that anionic ligands should exert the greatest splitting effect.
But anionic ligands are actually found at the low end of the
spectrochemical series.
✓ It does not take into account the covalent character of bonding
between the ligand and the central atom.

These weaknesses of CFT are explained by ligand field theory (LFT)

and molecular orbital theory (MOT).
 Colour in Coordination Compounds

❑ [Ti(H2O)6] 3+ is violet in colour. This is an octahedral complex where the

single electron (Ti3+ is a 3d1 system) in the metal d orbital is in the t2g level in
the ground state of the complex.
❑ The next higher state available for the electron is the empty eg level.
❑ If light corresponding to the energy of yellow-green region is absorbed by
the complex, it would excite the electron from t2g level to the eg level (t2g 1
eg 0 → t2g 0 eg 1 ). Consequently, the complex appears violet in colour.
❑ The crystal field theory attributes the colour of the coordination
compounds to d-d transition of the electron.
 Colour in Coordination Compounds
❑ For example, removal of water from [Ti(H2O)6]Cl3 on heating renders it colourless. Similarly,
anhydrous CuSO4 is white, but CuSO4.5H2O is blue in colour. This is because in the absence
of ligand, crystal field splitting does not occur and hence the substance is colourless.

❑ Influence of the ligand on the colour of a complex : If the didentate ligand, ethane-1,2-
diamine(en) is progressively added in the molar ratios en: Ni, 1:1, 2:1, 3:1, the following
series of reactions and their associated colour changes occur:
Metal Carbonyls
Structure of Metal Carbonyls
• The metal-carbon bond in metal
carbonyls possess both s and p
character.
• The M–C σ bond is formed by the
donation of lone pair of electrons on
the carbonyl carbon into a vacant
orbital of the metal.
• The M–C π bond is formed by the
donation of a pair of electrons from a
filled d orbital of metal into the vacant
antibonding π* orbital of carbon
monoxide.
• The metal to ligand bonding creates a
synergic effect which strengthens the
bond between CO and the metal.
Stability of Coordination Compounds
Assessment 3