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Q5.8:
List various types of isomerism possible for coordination compounds, giving an example of each.

Solution :

1. Structural Isomerism

Structural isomerism arises due to the difference in the arrangement of ligands around the central metal atom or the coordination sphere. It is categorized as follows:

Type Description Example
Ionization Isomerism The counter-ion replaces a ligand within the coordination sphere, producing different ions in solution. [Per Werner’s Theory] $[Co(NH_3)_5(SO_4)]Br$ and $[Co(NH_3)_5Br]SO_4$
Hydrate Isomerism Specific case of ionization isomerism where water molecules exchange positions between the coordination sphere and the solvent of crystallization. $[Cr(H_2O)_6]Cl_3$ and $[Cr(H_2O)_5Cl]Cl_2 \cdot H_2O$
Linkage Isomerism Arises in complexes containing ambidentate ligands (ligands that can coordinate through two different atoms). $[Co(NH_3)_5(NO_2)]Cl_2$ and $[Co(NH_3)_5(ONO)]Cl_2$
Coordination Isomerism Occurs in salts containing both cationic and anionic complex ions; the ligands exchange between metal centers. $[Co(NH_3)_6][Cr(CN)_6]$ and $[Cr(NH_3)_6][Co(CN)_6]$

2. Stereoisomerism

Stereoisomerism involves the same chemical formula and connectivity but differs in the spatial orientation of ligands. It is subdivided into:

A. Geometrical Isomerism

Arises due to restricted rotation of ligands about the metal center, primarily in square planar and octahedral complexes. [Based on VSEPR and Valence Bond Theory]

cis-[Pt(NH3)2Cl2] Cl NH3 Cl NH3 trans-[Pt(NH3)2Cl2] Cl NH3 NH3 Cl

B. Optical Isomerism

Occurs in chiral molecules that are non-superimposable mirror images of each other, known as enantiomers. They rotate plane-polarized light. [Per the Principle of Molecular Chirality]

  • Example: $[Co(en)_3]^{3+}$, where $en$ is ethylenediamine.
  • One isomer rotates light to the right (dextro-rotatory), the other to the left (laevo-rotatory).

Final Solution: The primary types of isomerism in coordination compounds are Structural Isomerism (Ionization, Hydrate, Linkage, Coordination) and Stereoisomerism (Geometrical and Optical).


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