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How does ligand exchange occur in transition metal complexes?

Ligand exchange in transition metal complexes is the process where one ligand in a complex is replaced by another ligand. This happens because transition metals can form coordinate covalent bonds with different ligands. Here’s a explanation:


1. Mechanism of Ligand Exchange

Ligand exchange can occur mainly by two types of mechanisms:

a) Associative mechanism (A):

  • A new ligand attaches to the metal first, temporarily increasing the coordination number.
  • Then, one of the original ligands leaves.
  • Common for smaller, less crowded metal complexes.

b) Dissociative mechanism (D):

  • A ligand leaves the metal first, creating a vacant site.
  • The new ligand then attaches to the metal.
  • Common for larger, crowded complexes.

Sometimes a combination of both (interchange mechanism, I) occurs.


2. Factors Affecting Ligand Exchange

  • Nature of the metal: Transition metals with high positive charge or small size exchange ligands more slowly.
  • Nature of the ligand: Ligands that form stronger bonds with the metal are less easily replaced.
  • Steric hindrance: Bulky ligands slow down ligand exchange.
  • Solvent and temperature: Polar solvents and higher temperatures can increase the rate of exchange.

3. Example in Words

  • In an aqueous solution, a water molecule in a metal complex can be replaced by an ammonia molecule:
    • Water leaves or ammonia attaches depending on the mechanism.

In short:
Ligand exchange is when one ligand in a transition metal complex is replaced by another, and it occurs via associative, dissociative, or intermediate mechanisms depending on the metal, ligand, and environment.

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