Seminar report on

ISOMERISM IN COORDINATION
COMPOUND

SUBMITTED BY

 Pragyan Chutia
CONTENT
1. Introduction.
2. Isomerism and their classification
3. Structural isomerism
Linkage isomerism
Ionisation isomerism
Solvate isomerism
Coordination isomerism
4. Steroisomerism
5. Geomatrical- cis trans
6. Optical isomerism
7. Conclusion.

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INTRODUCTION

Coordination compound are those compound which retain their

identities even when dissolved in water or any other solvent and their
Properties are completely different from those of constituent.
Coordination compound give rise to a wide variety of isomer due to
different types of linkage and different structural arrangements of
constituent atoms. The variety of coordination numbers in these
complexes provides a large number of isomers . As the coordination
number increases so does the number of possible isomers. we will focus
on the common coordination numbers, primarily 4 and 6. We will not
discuss isomerism where the ligands themselves are isomers

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Isomerism and to their classification

Isomerism in Coordination Compounds. Compounds having the same

chemical formula but a different arrangement of atoms are called
isomers. Because of the different arrangement of atoms, they differ in
one or more physical or chemical properties. There are two principal
types of isomerism in coordination .Compounds. A hierarchy of
classification is shown bellow-

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 Structural isomersim
Compounds having the same molecular formula but different
structural formulas are known as structural isomers and the
phenomenon is known as structural isomerism. Different types of
structural isomerisms are discussed bellow.

1. Ionisation Isomerism. In this type of isomerism, the difference

arises from the positions of groups within or outside the
coordination sphere. Therefore, these isomers give different ions
in solution, hence the name ionisation isomerism. For example,
there are two distinct compounds of the formula Co(NH3)5BrSO4.
One of them is red-violet and gives a precipitate with BaCl2
indicating that sulphate ion is outside the coordination sphere.
The second one is red and does not give precipitate with BaClz but
gives a precipitate of AgBr with silver nitrate indicating that now
bromide ion is outside the coordination sphere.The structures of
the two compounds and their modes of ionisation, therefore,
should be as follows :

Colour of Structure and mode of ionisation

the
compound
2−¿¿

Red violet [ CoBr ( N H 3 )5 ] S O4 → [ CoBr ( N H 3 )5 ]

2 +¿+S O 4 ¿

pentaamminebromo
Cobalt(iii) sulphate −¿¿
+¿+B r ¿
Red [ cos O 4 ( N H 3 )5 ] Br → [ cos O4 ( N H 3 )5 ]
Pentaammibesulphato
Cobalt(iii) bromide

2. Linkage Isomerism. In some ligands, there are two atoms which

can donate their lone pairs. For example, in NO2 ion, the nitrogen
atom as well as the oxygen atom can donate their lone pairs. This
gives rise to isomerism. If nitrogen donates its lone pair, one
particular compound will be formed. If oxygen does so, a different
compound (although having the same molecular formula) is

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obtained. For example, two different
pentaamminecobalt(III)chlorides, each containing the NO2 group in
the complex ion, have been prepared. These are :
As for example
Jørgensen discovered the first example of such behaviour in the
complex

3. Hydrate isomerism The compounds which have the same

molecular formula but differ by whether or not a solvent molecule is
directly bonded to the metal or present as free solvent molecules in
the crystal lattice are called solvate Isomers. This form of isomerism
is also known as ‘hydrate isomerism’ in the special case where water
is present as ligands or as molecules of hydration. For example:
[Cr(H2O)6]Cl3 and [Cr(H2O)5Cl]Cl2.H2O
4. Coordination Isomerism : In complexes when the cation and
anion both are complex ions, there may be exchange of ligands
between these two complex ions resulting in coordination. isomers.
In the pairs of these isomers, the central metal cation in the two
coordination sphere may be the same or different. Some examples of
coordination isomers are given below : (i) [Co (NH3 )6 ]
[ Cr(CN)6 ]and [Cr (NH3 )6 ][Co (CN)6]

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 Steroisomer
The isomers in which the same types and number of ligands are
coordinated to the metal atom or cation but with different spatial
arrangements are called steroisomers. In other words, steroisomers are
isomers that differ only in the spatial arrangement of ligands
coordinated to metal cation or atom.

Sterioisomerism is classified into two types :

Geometrical isomerism and Optical isomerism

Geometrical Isomerism
Sterioisomers in which the relative positions or orientations of the
ligands or more specifically donor atoms round the metal cation is
different are called geometrical isomers and this phenomenon is called
geometrical isomerism. Geometrical isomers can not be inter-conveted
without breaking of M-L bonds. Geometrical isomers exists only in pairs,
in one isomers the two particular ligands are adjacent to each other and
in the other the two are in opposite sides in the structural formula.
Thus, the isomer in which two particular ligands (either identical or
non-identical) occupy the adjacent positions of each other is called cis-
isomer and the isomer in which two particular ligands occupy opposite
positions to each other is called trans-isomer (The latin word cis means
next to, trans means across). Cis- and transisomers are different
compounds with different properties like melting points, dipole
moments, solubility, colours and chemical properties. For example, cis –
[Pt(NH3 )2 Cl2 ] is polar molecule and is more soluble in water than
trans-[Pt (NH3 )2Cl2 ]molecule which have zero dipole moment. Also cis
[Pt (NH3 )2Cl2 ] called cis-platin is an effective anti-cancer drug where
as the trans isomer is physiologically inactive. Geometrical isomerism is
most common in complexes having coordination number of 4 and 6. The
complexes which exhibit coordination numbers 2 and 3 do not exhibit
geometrical isomerism.

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 4.[ Mabcd] type:
Square planar complex of this type produce three isomer. The
structures of this isomers can be written by fixing the position of

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 one ligand (say,a) and placing other ligand b,c,d trans to it as
shown below.

Geometrical isomerism in complexes of coordination number 6. The

complexes having coordination number 6 adopt octahedral
geometry. The octahedral complexes also exhibit geometrical
isomerism. The complexes of the type Ma6 and Ma5b would not
show geometrical isomerism. The different types of octahedral
complexes exhibiting geometrical isomerism are discussed below.
a. Complex of the type Ma4b2 or Ma2b4 or Ma4bc show
geomatrical isomerism. As show below.

Complex of type MA3B4 is also exist in two isomeric form. The isomers of the compound
[RhCl3(py)3] are shown in below.

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 d. The complexes of the type [M(AA)2B2] or [M(AA)2BC] containing bidentate ligands
(aa) show geometrical isomerism. The other two ligands may be the same (B2) or
different (BC). The common examples are [M(en)2BC] where M is Co (III), Cr(III), Ir(III),
Rh(III), Pt(IV) and B and C are ligands such as NO2, I, Br, CI -, NH3, py, etc. For example,
the complex [Co(en)2Cl2]+, where en is H2NCH2CH,NH2, exists in cis and trans forms,
as shown in Fig.

Optical Isomerism
The complexes which can rotate the plane of the polarised light are optically active. The
isomer which can rotate the plane of the polarised light towards right is called dextro
rotatory whereas the isomer which can rotate the plane of the polarised light towards left is
called leavo rotatory. Optical isomers are mirror images that cannot be superimposed on
one another. These are called as enantiomers.
Optical isomers with coordination number:4
Tetrahedral complexes with coordination number 4 should exhibit optical isomerism
because there is no plane of symmetry in their molecules. However, this has not been found
to be the case. The first tetrahedral metal complex in which the central ion was surrounded
by four different ligands was prepared in 1963 but it has not been possible to resolve it into
d and / forms.

Square planar complexes are seldom optically active. This is because all the ligands and the
metal atom lie in the same plane. The molecule has a plane of symmetry (the plane of the
molecule is the plane of symmetry) and this cannot exhibit optical isomerism. One such
compound which has, however, been resolved into two forms is as shown.

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Optical isomerism with coordination number:6

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Complexes containing hexadentate ligands. The complexes containing hexadentate
ligands such ethylenediaminetetraacetato (EDTA) also show optical activity. For example,
the complex [Co(EDTA)] exists in two forms, d and l, as shown in Fig.
Complexes containing unidentate ligands. The complexes of the type [Mabcdef] are also
expected to show optical isomerism. A complex of this type can theoretically have 15
geometrical forms, each of which should be optically active.

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Reference
Miessler, G. L. & Donald, A. Tarr. Inorganic Chemistry 4 th Ed., Pearson, 2010
6. Atkin, P. Shriver & Atkins’ Inorganic Chemistry 5 th Ed. Oxford University Press
Puri,Sharma,Kalia Principles of inorganic Chemistry Vishal Publishing Co.

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