IRAM SHAHZADI

1725107027

ISOMERISM IN COORDINATION COMPOUNDS

Abstract:
The assembly of Co(NCS)2 with 1‐methyl‐1′‐(3‐pyridyl)‐2‐(4‐pyridyl)ethene (L1) exhibits a
novel supramolecular isomerism of [Co(L1)2(NCS)2]∞ caused by different placement
orientation of L1 around metal centers. The reaction in MeOH/H2O and EtOH/H2O resulted in
a double chain structure of 1, and that in EtOH/CH3NO2 led to an open framework structure
of 2. The reaction in MeOH/CH3NO2 solvent system concomitantly afforded 1 and 2. The
assemblies of 1‐(3‐pyridyl)‐2‐(4‐pyrimidyl)ethene (L2) with Co(NCS)2 created the water‐
coordinated complexes of Co(L2)2(H2O)2(NCS)2 (3 and 4), an MeOH coordinated complex of
Co(L2)2(H2O)2(NCS)2 (5), and an open framework coordination polymer of [Co(L1)2(NCS)2]∞ (6)
depending on the reaction solvent system. From these observations, it is suggested that in
the formation of 1, the solvent‐coordinated intermediate species would be generated first
and its trans coordination configuration should define the placement orientation of L1 in the
resulting polymer of 1. On the other hand, it is presumed that the solvent‐coordinated
intermediate would not be produced during the formation of 2 due to the weaker coordination
ability of EtOH and CH3NO2 molecules. The open framework coordination polymers of 2 and
6 are converted in the solid state into the isomeric coordination polymer of 1 and hydrogen
bonded network structure of 3, respectively.

ISOMERISM:
The existence of two or more chemical compounds with identical chemical composition but
different structures and properties is called isomerism.
Coordination compounds show a variety of isomerism which is more pronounced than that
shown by organic compounds.
The following types of isomerism are commonly found in coordination compounds:
1) Ionization isomerism
2) Coordination isomerism
3) Polymerization isomerism
4) Hydrate isomerism
5) Structural or salt isomerism
6) Stereoisomerism
7) Optical isomerism

1. Ionization isomerism:
The compounds having the same empirical formula with different ions in solution are said to
show ionization isomerization.
For example:
Violet [Co(NH3)5 Br]2+ SO4 and Red [Co(NH3)5 SO4] Br are ionization isomers which yield
sulphate and bromide ions, respectively.

2. Coordination isomerism:
In this type of isomerism the same number of coordinating groups may be
present in the complex but are linked to different metal ions. In these
complexes
[Co(NH3)6] [Cr(CN)6] and [Cr(NH3)6] [Co(CN)6]
(I) (II)
Cobalt is linked to NH3 in compounds (I) but linked to CN in (II).

3. Polymerization isomerism:
Compounds are said to have polymerization isomerism if their molecular
formulae are simple multiples of their stoichiometric arrangement.
For example:
[Pt (NH3)2 Cl2] and [Pt (NH3)4] [Pt Cl4]

4. Hydrate isomerism:
Water is a fairly strong coordinating group and would form many aquo
complexes. The number of water molecules which are directly linked to the
central metal ion and represented within the square brackets may vary. It
depends upon various factors and conditions. The variation in the number of
water molecules within the coordination sphere results in hydrate isomerism.
For example:
CrCl3.6H2O has three different isomeric forms depending upon the number of
H2O within the coordination sphere. The formula of these hydrates are:
[Cr(H2O)6]Cl3 [Cr(H2O)5]Cl2.H2O [Cr(H2O)4]Cl2].2H2O
(violet) (green) (green)

5. Structural or salt isomerism:

This type of isomerism results from two possible ways of linking coordinating
group to the central metal atom. NO2 group may either be attached to the
central metal atom or ion through N or O as shown below:

O
∕∕
M ─── N M ── O ── N = O
↘
 O

Nitro ── Nitrito ──

6. Stereoisomerism:
The isomerism which have same composition and molecular formula but
differ only in the relative positions of atoms or groups in space. This type of
isomerism is also called as geometrical isomerism. This type of isomerism is
also called as cis-trans isomerism and was predicted by Werner’s theory. This
type of isomerism is found in two compounds in cis-trans form is given
below:
 [Pt (NH3)2 Cl2] (coordination no. 4)
 [Co(NH3)4 Cl2] + (Coordination no. 6)
7. Optical isomerism:
The asymmetric molecules show the property of rotating the plane polarized
light either to left or right. Such molecules or compounds are said to be
optically active. The structures of these molecules are mirror images of one
another and are asymmetric.
For example:
The cis-[Co(NH3)4 Cl2] Cl is an asymmetric molecule and would be optically
active but trans-[Co(NH3)4 Cl2] Cl possesses symmetry and would not be
optically active.
Reference:
Dr,I.N.S etal.,2004.Novel Supramolecular Isomerism in Coordination Polymer
Synthesis from Unsymmetrical Bridging Ligands: Solvent Influence on the
Ligand Placement Orientation and Final Network Structure. Chemistry A
Eurpean Journel, 10: 3158-316