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What is ligand substitution in metal complexes?

Ligand substitution is a process in which one ligand (a molecule or ion attached to a metal ion in a complex) is replaced by another ligand. In other words, a ligand “swaps places” with a different one. This is a common type of reaction in coordination chemistry.

There are different ways this can happen:

  1. Associative mechanism – The new ligand attaches to the metal first, temporarily increasing the number of ligands around the metal, and then the old ligand leaves. This is common in square planar complexes.
  2. Dissociative mechanism – The original ligand leaves first, creating an empty spot for the new ligand to attach. This is common in octahedral complexes.
  3. Interchange mechanism – The old ligand leaves and the new ligand attaches at almost the same time.

Factors that influence ligand substitution include:

  • The type of metal ion (its size, charge, and electronic configuration).
  • The type of ligands (some ligands bind more strongly than others).
  • Steric effects (large ligands can block substitution).
  • The solvent, which can stabilize or destabilize intermediates.

A simple example is when a water molecule replaces another ligand in a metal complex, changing the complex’s properties.

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