22/07/2026
A short note ML4 type complex isomerism
Coordination complexes with a coordination number of 4 (represented as [ML 4 ] or mixed-ligand variations) adopt two distinct geometries: Square Planar (dsp 2 hybridization) and Tetrahedral (sp 3 hybridization).
How isomerism plays out depends entirely on geometry.
1. Square Planar Complexes
Square planar complexes lie flat in a single plane with bond angles of 90° and 180°.
Geometrical Isomerism (Cis / Trans)
Because positions adjacent (90°) and opposite (180°) exist in a plane, square planar complexes frequently exhibit geometrical isomerism:
[MA 4] and [MA 3 B] types: No geometrical isomers (all positions are equivalent relative to the unique ligand).
[MA2B2 ] type: 2 isomers
Cis-isomer: Identical ligands adjacent to each other (90° apart).
Trans-isomer: Identical ligands opposite to each other (180° apart).
Classic Example: Cisplatin (cis-[Pt(NH3)2Cl2]) is an effective chemotherapy drug, while its trans isomer is inactive.
[MA2BC] type: 2 isomers (cis and trans with respect to the two A ligands).
[MABCD] type: 3 isomers (Fix one ligand, e.g., A, and arrange B,C,D opposite to it).
[M(AB)2 ] type (unsymmetrical bidentate ligands, e.g., glycinate): 2 isomers (cis and trans).
Optical Isomerism
Generally optically inactive: Square planar complexes possess a plane of symmetry (σ) in the plane of the molecule itself.
Exception: Extremely rare cases where bulky, unsymmetrical chelating ligands disrupt this plane.
2. Tetrahedral Complexes
In a regular tetrahedron, all four ligand positions are equivalent and equidistant from one another (bond angles ≈109.5 ∘ ).
Geometrical Isomerism
Do NOT show geometrical isomerism: Since every position is adjacent to every other position, relative "cis" or "trans" arrangements are impossible.
Optical Isomerism
Normally optically inactive unless asymmetric.
[MABCD] type: If all four monodentate ligands are different, the molecule lacks a plane/center of symmetry, making it chiral. It forms non-superimposable mirror images (enantiomers).
Unsymmetric bidentate complexes: [M(AB)2] complexes with unsymmetrical chelates can also display optical activity.