Question
Explain different types of Structural isomerism with example.
✓
Answer
$(1)$ Linkage Isomerism:
$\rightarrow$ Linkage isomerism arises in a coordination compound containing ambidentate ligand.
$\rightarrow$ A simple example is provided by complexes containing the thiocyanate ligand, $ \text{NCS}^{-,}$ which may bind through the nitrogen to give $ \text{M-NCS}$ or through sulphur to give $ \text{M-SCN.}$
$\rightarrow$ Jorgenson discovered such behaviour in the complex $\left[ Co \left( NH _3\right)_5\left( NO _2\right)\right] Cl _2$, which is obtained as the red form, in which the nitrite ligand is bound through oxygen $( - ONO ),$ and as the yellow form, in which the nitrite ligand is bound through nitrogen $\left(- NO _2\right)$.
$\text { e.g. : }\left[ Co ( ONO )\left( NH _3\right)_5\right]^{2+} \text { and }\left[ Co \left( NO _2\right)\left( NH _3\right)_5\right]^{2+}$
$ \text{Red} \quad\text{Yellow}$
$(2)$ Coordination Isomerism:
$\rightarrow$ This type of isomerism arises from the interchange of ligands between cationic and anionic entities of different metal ions present in a complex.
e.g. : $\left[ Co \left( NH _3\right)_6\right]\left[ Cr ( CN )_6\right]$, and $\left[ Cr \left( NH _3\right)_6\right][ Co ( CN )_6$]
$(3)$ Ionisation Isomerism:
$\rightarrow$ 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.
e.g. : $ \left.\left. [Co \left( NH _3\right)_5\right]\left( SO _4\right)\right] Br \text { and }\left[ Cr \left( NH _3\right)_5 Br \right] SO _4$
$ {\left[ Pt \left( NH _3\right)_4 Cl _2\right] Br _2 \text { and }\left[ Pt \left( NH _3\right)_4 Br _2\right] Cl _2 }$
$ {\left[ Cr \left( NH _3\right)_4 Cl _2\right] NO _2 \text { and }\left[ Cr \left( NH _3\right)_4 Cl \cdot NO _2\right] Cl }$
$(4)$ Solvate Isomerism $OR$ Hydrate isomerism:
$\rightarrow$ This form of isomerism is known as 'hydrate isomerism' in case where water is involved as a solvent.
$\rightarrow$ This is similar to ionization isomerism.
$\rightarrow$ Three isomeric forms of $CrCl _3 \cdot 6 H _2 O$ are known
$(1)$ $\left[ Cr \left( H _2 O \right)_6\right] Cl _3$ $($violet$).$
$(2)$ $\left[ Cr \left( H _2 O \right)_5 Cl \right] Cl _2 \cdot H _2 O$ $($grey green$).$
$(3)$ $\left[ Cr \left( H _2 O \right)_4 Cl _2\right] Cl \cdot 2 H _2 O$ $($green$).$
$\rightarrow$ Linkage isomerism arises in a coordination compound containing ambidentate ligand.
$\rightarrow$ A simple example is provided by complexes containing the thiocyanate ligand, $ \text{NCS}^{-,}$ which may bind through the nitrogen to give $ \text{M-NCS}$ or through sulphur to give $ \text{M-SCN.}$
$\rightarrow$ Jorgenson discovered such behaviour in the complex $\left[ Co \left( NH _3\right)_5\left( NO _2\right)\right] Cl _2$, which is obtained as the red form, in which the nitrite ligand is bound through oxygen $( - ONO ),$ and as the yellow form, in which the nitrite ligand is bound through nitrogen $\left(- NO _2\right)$.
$\text { e.g. : }\left[ Co ( ONO )\left( NH _3\right)_5\right]^{2+} \text { and }\left[ Co \left( NO _2\right)\left( NH _3\right)_5\right]^{2+}$
$ \text{Red} \quad\text{Yellow}$
$(2)$ Coordination Isomerism:
$\rightarrow$ This type of isomerism arises from the interchange of ligands between cationic and anionic entities of different metal ions present in a complex.
e.g. : $\left[ Co \left( NH _3\right)_6\right]\left[ Cr ( CN )_6\right]$, and $\left[ Cr \left( NH _3\right)_6\right][ Co ( CN )_6$]
$(3)$ Ionisation Isomerism:
$\rightarrow$ 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.
e.g. : $ \left.\left. [Co \left( NH _3\right)_5\right]\left( SO _4\right)\right] Br \text { and }\left[ Cr \left( NH _3\right)_5 Br \right] SO _4$
$ {\left[ Pt \left( NH _3\right)_4 Cl _2\right] Br _2 \text { and }\left[ Pt \left( NH _3\right)_4 Br _2\right] Cl _2 }$
$ {\left[ Cr \left( NH _3\right)_4 Cl _2\right] NO _2 \text { and }\left[ Cr \left( NH _3\right)_4 Cl \cdot NO _2\right] Cl }$
$(4)$ Solvate Isomerism $OR$ Hydrate isomerism:
$\rightarrow$ This form of isomerism is known as 'hydrate isomerism' in case where water is involved as a solvent.
$\rightarrow$ This is similar to ionization isomerism.
$\rightarrow$ Three isomeric forms of $CrCl _3 \cdot 6 H _2 O$ are known
$(1)$ $\left[ Cr \left( H _2 O \right)_6\right] Cl _3$ $($violet$).$
$(2)$ $\left[ Cr \left( H _2 O \right)_5 Cl \right] Cl _2 \cdot H _2 O$ $($grey green$).$
$(3)$ $\left[ Cr \left( H _2 O \right)_4 Cl _2\right] Cl \cdot 2 H _2 O$ $($green$).$
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