Structural isomerism : Here the isomers have different arrangement of ligands around the central metal atom. It is of the following types :
(i) Ionisation isomerism : The co-ordination compound having the same composition or molecular formula but gives different ions in solution are called ionization isomers.
There takes place exchange of anions between the co-ordination sphere and ionization sphere.
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Example :
[CoBr(NH3)5]SO4
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[CoSO4(NH3)5]Br
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Pentaaminebromo cobalt (III) Sulphate
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Pentaaminesulphato cobalt (III) bromide
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SO42- present in ionisation sphere
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Br- present in ionization sphere
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Gives white precipitate with BaCl2
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Gives light yellow precipitate with AgNO3
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(ii) Co-ordination isomerism : In this case compound is made up of cation and anion and the isomerism arises due to interchange of ligands between complex cation and complex anion.
Example : [Co(NH3)6][Cr(CN)6]
[Cr(NH3)6][Co(CN)6]
hexaamine cobalt (III) hexacyano chromate (III) hexaamine chromium (III) hexacyanocobalt (III)
complex cation contains → NH3 ligand (with cobalt) complex anion contains → NH3 ligand (with chromium) complex anion contains → CN- ligand (with chromium) complex anion contains → CN- ligand (with cobalt)
(iii) Linkage isomerism : In this type of case isomers differ in the mode of attachment of ligand to central metal ion and the phenomenon is called linkage isomerism.
Example : [Co ONO(NH3)5]Cl2
Pentaamminenitritocobalt (III)
Pentaaminenitrocobalt (III) chloride
: O- No- oxygen atom donates lone pair of electrons (nitrito) NO2- nitrogen atom donates lone pair of electrons (nitro)
(iv) Hydrate isomerism : The hydrate isomers posses the same composition but differ in the number of water molecules present as ligands and the phenomenon is called hydrate isomerism.
Examples of it are as follows:
(a) [Cr(H2O)6]Cl3 hexaaquachromium (III) chloride (violet)
(b)[Cr(H2O)5Cl]Cl2.H2O pentaaquachlorochromium (III) chloride monohydrate (blue green)
(c) [Cr(H2O)4Cl]Cl2.2H2O tetraaquadichloro chromium (III) chloride dihydrate (green)
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