Isomerism

The word “isomers” literally means “equal units.” Isomers occur when compounds
having the same molecular formula have different chemical structures. Isomerism is
quite common in coordination compounds. Two or more compounds which have the
same chemical formula but different arrangement of atoms are called isomers. 

Types of isomerism

 Structural isomerism
o Linkage isomerism
o Solvate isomerism or hydrate isomerism
o Ionisation isomerism
o Coordination isomerism
 Stereoisomerism
o Geometrical isomerism
o Optical isomerism

Published by: Nabeel Yousaf (Content Writer)

Isomers differ in one (or) more physical or chemical properties because of the
difference in the arrangement of the atoms.
Isomerism in coordination compounds may be broadly divided into two types
structural isomerism and stereo isomerism.
Structural isomerism arises due to the presence of different kinds of bonds
between the metal and the ligands.

This further divided into several types: Ionisation isomerism, solvate

isomerism, ligand isomerism, linkage isomerism, polymerisation isomerism,
coordination isomerism and coordination position isomerism.

Structural isomerism: 

This type of isomerism arises due to the difference in structures of

coordination compounds. Structural isomerism, or constitutional
isomerism, is a form of isomerism in which molecules with the same
molecular formula have atoms bonded together in different orders.

Ionisation isomerism: 

This form of isomerism arises when the counter ion in a complex salt is itself a
potential ligand and can displace a ligand which can then become the counter ion.
he co-ordination compound having the same composition or molecular formula but
gives different ions in solution are called ionization isomers.
o Ionization isomers are identical except for a ligand has exchanged
places with an anion or neutral molecule that was originally outside the
coordination complex. The central ion and the other ligands are identical. For
example, an octahedral isomer will have five ligands that are identical, but the sixth

Published by: Nabeel Yousaf (Content Writer)

 will differ. The non-matching ligand in one compound will be outside of the
coordination sphere of the other compound. Because the anion or molecule outside
the coordination sphere is different, the chemical properties of these isomers is
different.
o There is exchange of anions between the co-ordination sphere and
ionization sphere.
o Examples: [Co(NH3)5Br] SO4 and [Co(NH3)5 SO4] Br

Solvate isomerism: 

o It is isomerism in which the solvent is involved as the ligand. If the

solvent is water, then it is called hydrate isomerism. This is also known as hydrate
isomerism if water is involved as a solvent.
o Compounds that have the same composition, but differ by whether (or)
not solvent molecules are present as ligands in the coordination sphere (or) are
merely present as free solvent molecules outside the coordination sphere are known
as solvate isomers.
o Example: [Cr(H2O)6]Cl3 and [CrCl2(H2O)4] Cl2.2H2O

Published by: Nabeel Yousaf (Content Writer)

 Linkage isomerism: 

o Linkage isomerism arises in a coordination compound

containing an ambidentate ligand. In the isomerism, a ligand can form
linkage with metal through different atoms.

o Examples: [Co(NH3)5ONO]Cl2 and [Co(NH3)5NO2]Cl2

Example –[Co(NH3 )5 (ONO)]2+ vs. [Co(NH3 )5 (NO2 )]2+

Published by: Nabeel Yousaf (Content Writer)

 Coordination isomerism: 

This type of isomerism arises from the interchange of ligands between

cationic and anionic entities of different metal ions present in a complex.

Examples: [Co(NH3)6][Cr(C2O4)3] and [Cr(NH3)6][Co(C2O4)3]

Published by: Nabeel Yousaf (Content Writer)

 Stereoisomerism: 
 
 This type of isomerism arises because of different spatial
arrangement.
 Compounds with the same chemical formula and chemical bonds, but
different arrangement of atoms (or) groups in space are called stereo
isomers. Stereo isomerism can be subdivided into geometrical
isomerism and optical isomerism.
 Geometrical isomerism is also known as cis-trans isomerism.
 The isomer in which the two identical groups are adjacent to each
other is known as a cis-isomer while the isomer in which the two
identical groups are diagonally opposite to each other is known as a
trans isomer.

Geometrical isomerism:

Published by: Nabeel Yousaf (Content Writer)

o  It arises in heteroleptic complexes due to different possible
geometrical arrangements of ligands.
o Differ in the spatial arrangements of the ligands,have different
chemical/physical properties different colors,melting points, polarities,
solubilities, reactivities, etc.

This isomerism arises due to the difference in geometrical arrangement of

the ligands around the central atom. When identical ligands occupy positions
opposite to each other called cis-isomer.  When identical ligands occupy
positions opposite to each other called trans –isomer. It is very common in
disubstituted complexes with co-ordination number of 4 and 6.

Complexes of co-ordination number 4

Tetrahedral geometry : In this case all the four ligands are symmetrically
arranged with respect to one another as such geometrical isomerism is not
possible.

Square planar geometry : The four ligands occupy position at the four corners
and the metal atom or ion is at the center and lie in the same plane.  

Published by: Nabeel Yousaf (Content Writer)

Note :   Square planar complexes of types Ma4, Ma3b, Mab3  do not exhibit
geometrical isomerism as all the spatial arrangements of the ligands relative
to each other are equivalent.

Complexes of co-ordination number 6

Octahedral geometry : Here the metal atom or ion lies at the center and 1 to 6
position are occupied by the ligands.  

Cis–Positions :  1–2, 2–3, 3–4, 4–5   

          Trans – Position : 1–4, 2–5, 3–6

         

Published by: Nabeel Yousaf (Content Writer)

 Optical isomerism:

Optical isomers are those isomers which are non-superimposable mirror

images. Optical isomers have the ability to rotate plane-polarized light in opposite
directions. Optical isomers exist when the molecules of the substances are mirror images
but are not superimposable upon one other.

Published by: Nabeel Yousaf (Content Writer)

(a)     Optical isomers are mirror images of each other and have chiral
centers. 

(b)     Mirror images are not super imposable and do and have the plane of
symmetry.

(c)      Optical isomers have similar physical and chemical properties but differ
in rotating the plane of plane polarized light.

(d)     Isomer which rotates the plane polarized light to the right is called
dextro rotatory (d-form) and the isomer which rotates the plane polarized light
to the left is called laevorotatory (l–form)

 Example : (a)  [Ma2b2c2]n+1 ; [Ma2b2c2]n+1 ; [Pt(Py)2(NH3)2Cl2]2+

Published by: Nabeel Yousaf (Content Writer)

(b)     [Ma b c e f] ; Pt(py) NH3NO2Cl Br]

Published by: Nabeel Yousaf (Content Writer)

Published by: Nabeel Yousaf (Content Writer)
Published by: Nabeel Yousaf (Content Writer)
Published by: Nabeel Yousaf (Content Writer)