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Substitution Reactions

The ligands of complex ions can be exchanged for other ligands. This is called a substitution reaction.

Common ligands

Common ligands

  • Some common ligands are water, NH3, and Cl-.
    • NH3 and water are of a similar size and have no charge.
    • Chloride ions are larger and have a negative charge.
Substitution reactions

Substitution reactions

  • Ligands can be exchanged.
    • A good example is the interconversion of [Cu(H2O)6]2+ and [Cu(NH3)6]2+
  • Substitution could also be incomplete.
    • E.g. [Cu(NH3)6]2+ to [Cu(NH3)4(H2O)2]2+
Coordination number

Coordination number

  • The coordination number can change in a ligand substitution reaction.
    • This usually happens when substituting ligands of a different size.
    • E.g. [Co(H2O)6]2+ + 4Cl- → [CoCl4]2-
  • The coordination number does not change when substituting water for ammonia because they are of a similar size.

The Chelate Effect

Some ligands can form multiple dative bonds with transition metal ions. This leads to some important chemical reactions.

Denticity

Denticity

  • Denticity describes the number of dative bonds that can be formed with a transition metal by one ligand:
    • A ligand that can form two bonds is called bidentate.
    • A ligand that can form one bond is called monodentate.
    • A ligand that can form multiple bonds is called multidentate.
  • Some common bidentate and multidentate ligands are on the next slide.
Multidentate ligands

Multidentate ligands

  • Binding sites are labelled by red circles.
The chelate effect

The chelate effect

  • Multidentate ligands will almost always replace monodentate ligands at a metal centre. This is called the chelate effect.
    • The chelate effect is largely an entropic effect.
    • When you substitute a multidentate ligand for a monodentate ligand, you increase the number of moles of molecules in the products of the reaction.
    • This leads to a large increase in entropy and this brings the Gibbs free energy below zero for the change.
Haem protein

Haem protein

  • The haem protein is found in red blood cells.
    • It has an iron(II) ion in the centre of a multidentate ligand.
    • In the lungs, oxygen binds to it as a ligand and can then be transported around the body by the protein.
    • In the body, the oxygen concentration is lower than in the lungs. So the dissociation of the oxygen is favoured.
Carbon monoxide

Carbon monoxide

  • When you inhale carbon monoxide, the CO can form a bond with the iron instead of oxygen.
  • CO forms an extremely strong bond with the iron. This will not break.
    • This means that the haem protein can no longer carry oxygen around the body.
    • This can starve the body of oxygen and cause death if enough is inhaled.
  • This is a ligand exchange reaction.
Jump to other topics
1

Physical Chemistry

1.1

Atoms, Molecules & Stoichiometry

1.2

Atomic Structure

1.3

Chemical Bonding

1.4

States of Matter

1.5

Chemical Energetics

1.6

Electrochemistry

1.7

Equilibria

1.8

Partition Coefficient

1.9

Reaction Kinetics

2

Inorganic Chemistry

3

Organic Chemistry & Analysis

3.1

Introduction to Organic Chemistry

3.2

Hydrocarbons

3.3

Halogen Derivatives

3.4

Hydroxy Compounds

3.5

Carbonyl Compounds

3.6

Carboxylic Acids & Derivatives

3.7

Nitrogen Compounds

3.8

Polymerisation

3.9

Analytical Techniques

3.10

Organic Synthesis

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