Isomerism in coordination compounds — geometrical and optical isomers

medium CBSE NEET NEET 2022 3 min read

Question

Explain geometrical and optical isomerism in coordination compounds with examples. Can [Co(en)2Cl2]+[\text{Co(en)}_2\text{Cl}_2]^+ show both types of isomerism?

(NEET 2022, similar pattern)


Solution — Step by Step

Geometrical isomerism arises when ligands can be arranged differently in space around the central metal ion, leading to cis (same side) and trans (opposite side) forms.

Condition: The complex must have at least two different types of ligands in a square planar or octahedral geometry.

Example: [Pt(NH3)2Cl2][\text{Pt(NH}_3)_2\text{Cl}_2] (square planar)

  • cis isomer: both Cl atoms on the same side
  • trans isomer: Cl atoms on opposite sides

Note: Tetrahedral complexes do NOT show geometrical isomerism (all positions are equivalent).

Optical isomerism occurs when a complex and its mirror image are non-superimposable. Such pairs are called enantiomers. One rotates plane-polarised light clockwise (dextro, d) and the other anticlockwise (laevo, l).

Condition: The complex must lack a plane of symmetry and a centre of symmetry (it must be chiral).

This is most commonly seen in octahedral complexes with bidentate ligands like ethylenediamine (en).

This is an octahedral complex with 2 bidentate en ligands and 2 monodentate Cl⁻ ligands.

Geometrical isomerism: Yes.

  • cis isomer: both Cl⁻ on the same side (adjacent positions)
  • trans isomer: both Cl⁻ on opposite sides (180° apart)

Optical isomerism: Only the cis isomer shows optical isomerism (it has no plane of symmetry). The trans isomer has a plane of symmetry and is optically inactive.

So [Co(en)2Cl2]+[\text{Co(en)}_2\text{Cl}_2]^+ has three isomers in total: cis-d, cis-l, and trans.


Why This Works

Geometrical isomerism is about spatial arrangement — same connectivity but different 3D positioning. Optical isomerism is about chirality — the molecule and its mirror image cannot be superimposed.

The trans isomer of [Co(en)2Cl2]+[\text{Co(en)}_2\text{Cl}_2]^+ has a mirror plane passing through the two Cl atoms and the Co centre, making it achiral. The cis isomer lacks such a plane — the en ligands wrap around the metal in a way that creates a chiral centre, giving rise to d and l forms.


Alternative Method — Quick Rules

GeometryGeometrical IsomerismOptical Isomerism
TetrahedralNoPossible (rare)
Square planarYes (for [Ma2b2][Ma_2b_2])No (planar = has symmetry plane)
OctahedralYesYes (especially with bidentate ligands)

For NEET, remember: [Co(en)3]3+[\text{Co(en)}_3]^{3+} shows only optical isomerism (no geometrical — all ligands are identical bidentate). [Co(en)2Cl2]+[\text{Co(en)}_2\text{Cl}_2]^+ shows both geometrical and optical isomerism. These two are the most frequently tested examples.


Common Mistake

Students often claim that the trans isomer of [Co(en)2Cl2]+[\text{Co(en)}_2\text{Cl}_2]^+ also shows optical isomerism. It does NOT. The trans isomer has a plane of symmetry and is superimposable on its mirror image. Only the cis isomer is chiral. Always check for a symmetry plane before claiming optical activity.

Want to master this topic?

Read the complete guide with more examples and exam tips.

Go to full topic guide →

Try These Next