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Q.The compounds [Co(SO4)(NH3)5]Br[Co(SO_4)(NH_3)_5]Br and [Co(Br)(NH3)5]SO4[Co(Br)(NH_3)_5]SO_4 represent : (A) optical isomerism (B) linkage isomerism (C) ionisation isomerism (D) coordination isomerism

CBSECBSE Class XII Board 2023MCQ· 1mImportance★★★★★
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The two compounds have the same molecular formula but differ in which anion is bound to the metal (inside the coordination sphere) and which is free (outside). This is the defining feature of ionisation isomerism, so the correct answer is option (C).

Why this is about ionisation isomerism

In coordination chemistry, isomerism arises when two or more compounds share the same overall formula but differ in how atoms or groups are arranged. The key question here is: which ions are directly bonded to the central metal, and which are free in solution?

Ionisation isomerism occurs specifically when the same set of ligands and counter-ions can be swapped between the coordination sphere and the ionic lattice. The two isomers produce different ions when dissolved — hence the name “ionisation” isomerism.

Let’s look at the two compounds:

  1. First compound: [Co(SO4)(NH3)5]Br[Co(SO_4)(NH_3)_5]Br

    • Inside the square brackets: cobalt(III) is bonded to five ammonia molecules and one sulfate ion (SO42−SO_4^{2-}).
    • Outside the brackets: a bromide ion (Br−Br^-) is the free counter-ion.
    • When dissolved, this compound will release Br−Br^- ions into solution.
  2. Second compound: [Co(Br)(NH3)5]SO4[Co(Br)(NH_3)_5]SO_4

    • Inside the brackets: cobalt(III) is bonded to five ammonia molecules and one bromide ion (Br−Br^-).
    • Outside: a sulfate ion (SO42−SO_4^{2-}) is free.
    • On dissolution, this compound releases SO42−SO_4^{2-} ions.
Watch out

A common mistake is to think these are linkage isomers. Linkage isomerism requires a ligand that can bind through two different atoms (like NO2−NO_2^- binding through N or O). Here, SO42−SO_4^{2-} and Br−Br^- are different ligands entirely — they are not the same group binding in two ways. So linkage isomerism does not apply.

Step-by-step reasoning

  1. Check the molecular formula

    Both compounds contain one Co, one Br, one SO₄, and five NH₃ groups. Their overall composition is identical: [CoBr(SO4)(NH3)5][CoBr(SO_4)(NH_3)_5]. This rules out any isomerism that requires a different atomic makeup (like structural isomerism in organic compounds).

  2. Identify the coordination sphere

    In the first compound, the sulfate is inside the coordination sphere (bonded to Co), and bromide is outside. In the second, bromide is inside and sulfate is outside. The set of ligands directly attached to the metal is different in each case.

  3. Predict the ions produced in solution

    • Compound 1: [Co(SO4)(NH3)5]Br→[Co(SO4)(NH3)5]++Br−[Co(SO_4)(NH_3)_5]Br \rightarrow [Co(SO_4)(NH_3)_5]^+ + Br^-
    • Compound 2: [Co(Br)(NH3)5]SO4→[Co(Br)(NH3)5]2++SO42−[Co(Br)(NH_3)_5]SO_4 \rightarrow [Co(Br)(NH_3)_5]^{2+} + SO_4^{2-} …

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