CHAPTER -03

Coordination Compounds

Coordination compounds are those molecular compounds which

retain their identity in solid state as well as in dissolved state. In
these compounds, the central metal atom or ion is linked by ions
or molecules with coordinate bonds. e.g. potassium
ferrocyanide, 𝐾4 [𝐹𝑒(𝐶𝑁)6 ].
𝑎𝑞
𝐾4 [𝐹𝑒(𝐶𝑁)6 ] ⇌ 4𝐾 + + [𝐹𝑒(𝐶𝑁)6 ]4−

Central metal atom

Ligands
𝐾4 [𝐹𝑒(𝐶𝑁)6 ] Coordination sphere (entity)

Counter ion Coordination number

Double Salts
These are the addition molecular compounds which are stable in
solid state but dissociate into constituent ions in the solution.
e.g. Mohr’s salt, [𝐹𝑒𝑆𝑂4 ⋅ (𝑁𝐻4 )2 𝑆𝑂4 ⋅ 6𝐻2 𝑂] get dissociated into
𝐹𝑒 2+ , 𝑁𝐻4+ and 𝑆𝑂42− ions.

Terms Related to Coordination Compounds

1. Complex Ion or Coordination Entity
It is an electrically charged species in which central metal
atom or ion is surrounded by number of ions or neutral
molecules.
(i) Cationic complex entity It is the complex ion which
carries positive charge, e.g. [𝑃𝑡(𝑁𝐻3 )4 ]2+ .
(ii) Anionic complex entity It is the complex ion which
carries negative charge, e.g. [𝐹𝑒(𝐶𝑁6 )]4− .
2. Central Atom or Ion
The atom or ion to which a fixed number of ions or groups are
bound, is called central atom or ion. It is also referred as Lewis
acid. e.g. in [𝑁𝑖𝐶𝑙2 (𝐻2 𝑂)4 ], 𝑁𝑖 is central metal atom. It is
generally transition element or inner-transition element.
These central atoms/ions are also referred to as Lewis acids.

3. Ligands
Ligand is electron donating species (ions or molecules) bound
to the central atom in the coordination entity.
These may be charged or neutral. Ligands are of the following
types:
(i) Unidentate It is a ligand, which has one donor site, i.e.
the ligand bound to a metal ion through a single donor
site, e.g. 𝐻2 𝑂, 𝑁𝐻3 , etc.
(ii) Didentate It is the ligand, which has two donor sites.
e.g.

(iii) Polydentate It is the ligand, which has several donor

sites. e.g. [𝐸𝐷𝑇𝐴]4 is hexadentate ligand.

(iv) Ambidentate ligands These are the monodentate ligands

which can ligate through two different sites, e.g. 𝑁𝑂2 , 𝑆𝐶𝑁,
etc.
 (v) Chelating ligands Di or polydentate ligands cause
cyclisation around the metal atom which are known as
chelates. Such ligands uses two or more donor atoms to
bind a single metal ion and are known as chelating
ligands.
More the number of chelate rings, more is the stability of
complex.
The stabilisation of coordination compounds due to
chelation is known as chelate effect.

𝜋-acid ligands are those ligands which can form 𝜎-bond and
𝜋-bond by accepting an appreciable amount of 𝜋 electron
∗
density from metal atom pulling facts to empty 𝜋 or 𝜋 -orbitals.
4. Coordination Number
It is defined as the number of coordinate bonds formed by
central metal atom, with the ligands.
e.g. in [𝑃𝑡𝐶𝑙6 ]2 , 𝑃𝑡 has coordination number 6.
In case of monodentate ligands,
Coordination number = number of ligands
In polydentate ligands,
Coordination number = number of ligands × denticity
5. Coordination Sphere
The central metal/ion and the ligands attached to it, are
enclosed in square bracket which is known as coordination
sphere. The ionisable group written outside the bracket is
known as counter ions.
6. Coordination Polyhedron
The spatial arrangement of the ligands which are directly
attached to the central atom or ion, is called coordination
polyhedron around the central atom or ion. e.g. [𝐶𝑂(𝑁𝐻3 )6 ]3+
is octahedral, [𝑁𝑖(𝐶𝑂)4 ] is tetrahedral and [𝑃𝑡𝐶𝑙4 ]2 is square
planar.
7. Oxidation Number of Central Atom
The charge of the complex if all the ligands are removed along
with the electron pairs that are shared with the central atom,
is called oxidation number of central atom.
e.g. [𝐶𝑢(𝐶𝑁)4 ]3 , oxidation number of copper is +1, and
represented as 𝐶𝑢(𝐼).
Types of Complexes
Homoleptic Complexes
Complexes in which the metal atom or ion is linked to only one
kind of donor atoms, are called homoleptic complexes. e.g.
[𝐶𝑜(𝑁𝐻3 )6 ]3+.
Heteroleptic Complexes
Complexes in which the metal atom or ion is linked to more than
one kind of donor atoms are called heteroleptic complexes. e.g.
[𝐶𝑂(𝑁𝐻3 )4 𝐶𝑙2 ]+ .
Labile and Inert Complexes
Complexes in which the ligand substitution is fast are known as
labile complexes and in which ligand substitution is slow, are
known as inert complexes.
Effective Atomic Number (EAN)
This concept was proposed by Sidgwick. In a complex, the EAN
of metal atom is equal to the total number of electrons present
in it.
𝐸𝐴𝑁 = 𝑍 − 𝑂𝑁 of metal + 2 × 𝐶𝑁
(where, 𝑍 = atomic number of metal atom
𝑂𝑁 = oxidation number of metal
and 𝐶𝑁 = coordination number of complex)
An ion with central metal atom having EAN equal to next inert
gas will be more stable.
IUPAC Naming of Complex Compounds
Naming is based on set of rules given by IUPAC.
1. Name of the compound is written in two parts (i) name of
cation, and (ii) name of anion.
2. The cation is named first in both positively and negatively
charged coordination complexes.
3. The dissimilar ligands are named in an alphabetical order
before the name of central metal atom or ion.
4. For more then one similar ligands, the prefixes di, tri, tetra,
etc are added before its name. If the di, tri, etc already appear
in the complex then bis, tris, tetrakis are used.
5. If the complex part is anion, the name of the central metal
ends with suffix ‘ate’.
6. Names of the anionic ligands end in ‘O’, names of positive
ligands end with ‘ium’ and names of neutral ligands remains
as such. But exception are there as we use aqua for 𝐻2 𝑂,
ammine for 𝑁𝐻3 , carbonyl for 𝐶𝑂 and nitrosyl for 𝑁𝑂.
7. Oxidation state for the metal in cation, anion or neutral
coordination compounds is indicated by Roman numeral in
parentheses.
8. The name of the complex part is written as one word.
9. If the complex ion is a cation, the metal is named same as the
element.
10. The neutral complex molecule is named similar to that of the
complex cation.
Some examples are
(i) [𝐶𝑟(𝑁𝐻3 )3 (𝐻2 𝑂)3 ]𝐶𝑙3
triamminetriaquachromium (III) chloride
(ii) [𝐶𝑂(𝐻2 𝑁𝐶𝐻2 𝐶𝐻2 𝑁𝐻2 )3 ]2 (𝑆𝑂4 )3
tris (ethane-1,2-diammine) cobalt (III) sulphate
(iii) [𝐴𝑔(𝑁𝐻3 )2 ][𝐴𝑔(𝐶𝑁)2 ]
diamminesilver (I) dicyanoargentate(I)
(iv) 𝐾4 [𝐹𝑒(𝐶𝑁)6 ]
potassiumhexacyanoferrate (II)
Isomerism in Coordination Compounds
Coordination compounds exhibit the following types of
isomerism:
1. Structural Isomerism
In this isomerism, isomers have different bonding pattern.
Different types of structural isomers are
(i) Linkage isomerism This type of isomerism is shown by
the coordination compounds having ambidentate ligands.
e.g.[𝐶𝑜(𝑁𝐻3 )5 (𝑁𝑂2 )]𝐶𝑙 and [𝐶𝑜(𝑁𝐻3 )5 (𝑂𝑁𝑂)]𝐶𝑙 or
pentammine nitrito-N-cobalt (III) chloride and
pentamminenitrito-O-cobalt (III) chloride.
(ii) Coordination isomerism This type of isomerism arises
from the interchange of ligands between cationic and
anionic complexes of different metal ions present in a
complex, e.g.
[𝐶𝑟(𝑁𝐻3 )6 ] [𝐶𝑜(𝐶𝑁)6 ] and [𝐶𝑜(𝑁𝐻3 )6 ] [𝐶𝑟(𝐶𝑁)6 ]
(iii) Ionisation isomerism This isomerism arises due to
exchange of ionisable anion with anionic ligand, e.g.
[𝐶𝑜(𝑁𝐻3 )5 𝑆𝑂4 ]𝐵𝑟 and [𝐶𝑜(𝑁𝐻3 )5 𝐵𝑟]𝑆𝑂4
(Red) (Violet)
(iv) Solvate isomerism This is also known as hydrate
isomerism. In this isomerism, water is taken as solvent. It
has different number of water molecules in the
coordination sphere and outside it, e.g.
[𝐶𝑜(𝐻2 𝑂)6 ]𝐶𝑙3 , [𝐶𝑜(𝐻2 𝑂)4 𝐶𝑙2 ]𝐶𝑙 ⋅ 2𝐻2 𝑂, [𝐶𝑜(𝐻2 𝑂)3 𝐶𝑙3 ] ⋅ 3𝐻2 𝑂
2. Stereoisomerism
Stereoisomers have the same chemical formula and chemical
bonds but they have different spatial arrangement. These are
of two types :
(i) Geometrical isomerism Geometrical isomers are further
of two types i.e. cis and trans isomers. This isomerism is
common in complexes with coordination number 4 and 6.
Geometrical isomerism in complexes with
coordination number 4
(i) Tetrahedral complexes do not show geometrical isomerism.
(ii) Square planar complexes of formula [𝑀𝑋2 𝐿2 ] (𝑋 and 𝐿 are
unidentate) show geometrical isomerism. The two 𝑋 ligands
may be arranged adjacent to each other in a cis isomer, or
opposite to each other in a trans-isomer, e.g.

(iii) Square planar complex of the type [MABXL] (where A, B, X,

L, are unidentate ligands) shows three isomers, two cis and
one trans.
The structures of these isomers can be written by fixing the
position of one ligand and placing other ligands trans to it.

e.g. [𝑃𝑡(𝑁𝐻3 )(𝐵𝑟)(𝐶𝑙)(𝑃𝑦)]

Geometrical isomerism in complexes with coordination
number 6
Octahedral complexes of formula [𝑀𝑋2 𝐿4 ], in which the two X
ligands may be oriented cis or trans to each other, e.g.
[𝐶𝑜(𝑁𝐻3 )4 𝐶𝑙2 ]+ .

Octahedral complexes of formula [𝑀𝑋2 𝐴2 ], where 𝑋 are unidentate

ligands and A are didentate ligand, form cis and trans isomers,
e.g. [𝐶𝑜𝐶𝑙2 (𝑒𝑛)2 ].
In octahedral complexes of formula [𝑀𝐴3 𝑋3 ], if three donor atoms
of the same ligands occupy adjacent positions at the corners of
an octahedral face, it is known as facial (fac) isomer, when the
positions are around the meridian of the octahedron, it is known
as meridional (mer) isomer. e.g. [𝐶𝑜(𝑁𝐻3 )3 (𝑁𝑂2 )3 ]

(ii) Optical isomerism These are the complexes which have

chiral structures. It arises when mirror images cannot be
superimposed on one another. These mirror images are
called enantiomers. The two forms are called dextro (d)
and laevo (l) forms.
Tetrahedral complexes with formula [𝑀(𝐴𝐵)2 ] show
optical isomers and octahedral complexes (cis form)
exhibit optical isomerism.
Bonding in Coordination Compounds
Werner’s Theory
Metals exhibit two types of valencies in the formation of
complexes. These are primary valencies and secondary valencies.
1. Primary valencies correspond to oxidation number (ON) of the
metal and are satisfied by anions. These are ionisable and
non-directional.
2. Secondary valencies correspond to coordination number (CN)
of the metal atom and are satisfied by ligands. These are non-
ionisable and directional. Hence, geometry is decided by these
valencies.
3. Metal ion should satisfy both primary and secondary
valancies.
Limitations
Werner theory was unable to account for the following.
(i) Definite geometry of coordination compounds.
(ii) Presence of magnetic and optical properties of coordination
compounds.
To overcome the limitations of Werner’s theory, various theories
were put forward such as valence bond theory, cyrstal field
theory.
Valence Bond Theory (VBT)
This theory was proposed by L. Pauling in 1930 s. According to
this theory, when a complex is formed, the metal ion/atom
provides empty orbitals to the surrounding ligands. Coordination
number shows the number of such empty orbitals, i.e. number of
empty orbitals is equal to the coordination number. These empty
orbitals hybridised before participation in bonding and the nature
of hybridisation depends on the nature of metal and on the
nature of approaching ligand.
Inner orbital Complexes or Outer Orbital Complexes
When outer d-orbital nd shells are used in bonding, the
complexes are called outer orbital complexes. They are formed
due to weak field ligands or high spin ligands and hybridisation
is 𝑠𝑝3 𝑑2. They have octahedral geometry.
When d-orbitals of (n – 1) shell are used, these are known as
inner orbital complex.
They are formed due to strong field ligands or low spin ligands
and hybridisation is 𝑑2 𝑠𝑝3 . They have also octahedral geometry.
1. 6-ligands (unidentate), octahedral entity
(i) Inner orbital complex [𝐶𝑜(𝑁𝐻3 )6 ]3+
All electrons are paired, therefore complex will be diamagnetic
in nature.
(ii) Outer orbital complex, [𝑪𝒐𝑭𝟔 ]𝟑−

Complex has unpaired electrons, therefore, it will be

paramagnetic in nature.
2. 4-ligands (unidentate) tetrahedral entity
S. No. Inner orbital complexes Outer orbital complexes
(a) Strong field or low spin Wake field or high spin
ligands ligands
 (b) Hybridisation is 𝑑𝑠𝑝2 Hybridisation is 𝑠𝑝3
(where one orbital of 3𝑑, (where one orbital of 4𝑠
one orbital of 4𝑠 and two and three orbitals of 4𝑝)
orbitals of 4𝑝)
(c) Square planar shape Tetrahedral shape
(i) Inner orbital complex, [𝑁𝑖(𝐶𝑁)4 ]2

All electrons are paired so complex will be diamagnetic in nature.

(ii) Outer orbital complex, [𝐶𝑜𝐶𝑙4 ]

Since, complex has unpaired electrons, so it will be paramagnetic

in nature.
Limitations of VBT
This theory could not explain the quantization of the magnetic
data, existence of inner orbital and outer orbital complex, change
of magnetic moment with temperature and colour of complexes.
Crystal Field Theory (CFT)
This theory was proposed by H. Bethe in 1929 and van Vleck.
Orgel, in 1935, applied this theory to coordination compounds.
In this theory, ligands are treated as point charges in case of
anions and dipoles in case of neutral molecules.
The five d-orbitals are classified as
(i) Three d-orbitals i.e. 𝑑𝑥𝑦 , 𝑑𝑦𝑧 and 𝑑𝑧𝑥 are oriented in
between the coordinate axes and are called 𝑡2𝑔 -orbitals.
(ii) The other two d-orbitals, i.e. 𝑑𝑥 2 𝑦2 and 𝑑𝑧2 oriented along
the axes are called 𝑒𝑔 -orbitals.
Due to approach of ligands, the five degenerate d-orbitals split.
Splitting of d-orbitals depends on the nature of the crystal field.

The energy difference between 𝑡2𝑔 and 𝑒𝑔 level is designated

by Δ and is called crystal field splitting energy.

By using spectroscopic data for a number of coordination

compounds, having the same metal ions but different ligand, the
crystal field splitting for each ligand has been calculated. A series
in which ligand are arranged in order of increasing magnitude of
crystal field splitting, is called spectrochemical series.
Spectrochemical series
𝐼 < 𝐵𝑟 < 𝑆𝐶𝑁 < 𝐶𝑙 < 𝑆 2 < 𝐹 < 𝑂𝐻 < 𝐶2 𝑂42− < 𝐻2 𝑂 < 𝑁𝐶𝑆 −
< 𝐸𝐷𝑇𝐴4− < 𝑁𝐻3 < 𝑒𝑛 < 𝐶𝑁 − < 𝐶𝑂.
Crystal Field Splitting in Octahedral Complexes
In case of octahedral complexes, energy separation is denoted
by Δ0 (where subscript 𝑜 is for octahedral).
In octahedral complexes, the six-ligands approach the central
metal ion along the axis of 𝑑𝑥 2 𝑦2 and 𝑑𝑧2 orbitals. These are 𝑒𝑔
orbitals.
Energy of 𝑒𝑔 set of orbitals > energy of 𝑡2𝑔 set of orbitals.
The energy of 𝑒𝑔 orbitals will increase by (3/5)Δ0 and 𝑡2𝑔 will
decrease by (2/5)Δ0 .
If Δ0 < 𝑃, the fourth electron enters one of the 𝑒𝑔 orbitals giving
3 1
the configuration 𝑡2𝑔 𝑒𝑔 . Ligands for which Δ0 < 𝑃 are known as
weak field ligands and form high spin complexes.
If Δ0 > 𝑃, it becomes more energetically favourable for the fourth
4
electron to occupy a 𝑡2𝑔 orbital with configuration 𝑡2𝑔 𝑒𝑔∘ . (where,
𝑃 = energy required for 𝑒 pairing in an orbital). Ligands which
produce this effect are known as strong field ligands and form low
spin complexes.
Crystal Field Splitting in Tetrahedral Complexes
In tetrahedral complexes, four ligands may be imagined to occupy
the alternate corners of the cube and the metal ion at the center
of the cube.
In such complexes 𝑑-orbital splitting is inverted and is smaller
as compared to the octahedral field splitting.
Energy of 𝑡2 set of orbitals > Energy of 𝑒 set of orbitals.
Orbital splitting energies are so low that pairing of electrons are
not possible so these form high spin complexes.

Colour in Coordination Compounds

The crystal field theory attributes the colour of the coordination
compounds due to 𝑑-𝑑 transition of the electron, i.e. electron
jump from 𝑡2𝑔 level to higher 𝑒𝑔 level.
In the absence of ligands, crystal field splitting does not occur
and hence the substance is colourless.
e.g. [𝑇𝑖(𝐻2 𝑂]6 ]3+ — Violet in colour
[𝐶𝑢(𝐻2 𝑂)4 ]2+ — Blue in colour, etc.
Limitations of CFT
1. It does not consider the formation of p bonding in
complexes.
2. It is also unable to account satisfactorily for the relative
strengths of ligands, e.g. it does not explain why 𝐻2 𝑂 is
stronger ligand than 𝑂𝐻.
3. It gives no account of the partialy covalent nature of metal-
metal bonds.
Ligand Field or Molecular Orbital Theory
This theory was put forward by Hund and Mulliken. According to
this theory, all the atomic orbitals of the atom participating in
molecule formation get mixed to give rise an equivalent number
of new orbitals, called the molecular orbitals. The electrons are
now under the influence of all the nuclei.
Stability of Coordination Compounds
The stability of complex in solution refers to the degree of
association between the two species involved in the state of
equilibrium. It is expressed as stability constant (𝐾 ).
[(𝑀𝐿 )𝑦 ]
e.g. 𝑀+ + 𝑛𝐿𝑥 ⇌ [𝑀𝐿𝑛 ]𝒚 ; 𝑛
𝐾 = [𝑴+][𝑳 𝒙 ]𝒏

The factors on which stability of the complex depends :

(i) Charge on the central metal atom As the magnitude of
charge on metal atom increases, stability of the complex
increases.
(ii) Nature of metal ion The stability order is 3𝑑 < 4𝑑 < 5𝑑
series.
(iii) Basic nature of ligands Strong field ligands form stable
complex.
The instability constant or the dissociation constant of
compounds is defined as the reciprocal of the formation or
stability constant.
Importance and Applications of Coordination
Compounds
1. They are used in many qualitative and quantitative
analysis.
2. Hardness of water is estimated by simple titration with
𝑁𝑎2 EDTA.
3. Purification of metals can be achieved through formation
and subsequent decomposition of their coordination
compounds.
4. They have great importance in biological systems.
5. They are used as catalyst for many industrial processes.
6. In medicinal chemistry, there is a growing interest of
chelating therapy.
Organometallic Compounds
They contain one or more metal-carbon bond in their molecules.
They are of the following types:
1. Sigma (𝝈) Bonded Compounds
Metal-carbon bond is sigma bond, e.g. (𝐶2 𝐻5 )4 𝑃𝑏, 𝑍𝑛(𝐶2 𝐻5 )2 ,
𝑅—Mg—𝑋, etc.
2. Pi(𝝅) Bonded Compounds
In which molecules/ions containing 𝜋 bonds act as a ligand,
e.g. ferrocene, dibenzene chromium and Zeise’s salt.

Zeise's salts is 𝐾[𝑃𝑡𝐶𝑙3 (𝜂 2 − 𝐶2 𝐻4 )] in which ethylene acts as a

ligand which do not have a lone pair of electron.
In ferrocene, 𝐹𝑒(𝜂 5 − 𝐶5 𝐻5 )2 , 𝜂 represents the number of
carbon atoms with which metal ion is directly attached.
3. 𝝈 and 𝝅 Bonded Compounds
Metal carbonyls are their examples. Metal-carbon bond of
metal carbonyls have both c and n-bond character. They
have CO molecule as ligand, e.g.
Wilkinson's catalyst (𝑅ℎ(𝑃𝑃ℎ3 )3 𝐶𝑙] is used as homogeneous
catalyst in the hydrogenation of alkenes. Zeigler-Natta catalyst
[𝑇𝑖𝐶𝑙4 + (𝐶2 𝐻5 )3 𝐴𝑙] acts as heterogeneous catalyst in the
polymerisation of ethylene.