What is the Difference Between Oxidative Addition and Reductive Elimination?

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Oxidative addition and reductive elimination are two types of reactions that involve a change in the oxidation state and coordination number of a metal center in a coordination complex. They are related processes, but they have opposite effects:

Oxidative Addition:

  • Involves the addition of two anionic ligands to a metal center.
  • Results in an increase in the oxidation state and coordination number of the metal.
  • Facilitated by electron-rich metal centers having low oxidation states.
  • Commonly observed for four- and five-coordinate complexes, as they have vacant coordination sites.
  • Often occurs in catalytic cycles, in conjunction with its reverse reaction, reductive elimination.

Reductive Elimination:

  • Involves the removal of two anionic ligands from a metal complex.
  • Results in a decrease in the oxidation state and coordination number of the metal.
  • Facilitated by electron-poor metal centers having high oxidation states.
  • Intramolecular reaction, favored by low electron density of the metal.
  • Ligands must be in a cis position in order to undergo reductive elimination.

These two reactions are crucial in various applications, such as catalytic cycles and product-releasing steps in several reactions that form C-H and C-C bonds.

Comparative Table: Oxidative Addition vs Reductive Elimination

Here is a table comparing oxidative addition and reductive elimination:

Property Oxidative Addition Reductive Elimination
Definition Oxidative addition is a chemical reaction where two anionic ligands are attached to a metal center, increasing its oxidation state by two units. Reductive elimination is the opposite reaction, where two anionic ligands leave the coordination complex, decreasing the oxidation state and coordination number of the metal.
Type of Ligands Involves the addition of two A-B type anionic ligands. Involves the removal of two anionic ligands.
Coordination Number Increases by two units. Decreases by two units.
Oxidation State of the Metal Increases by two units. Decreases by two units.
Mechanisms There are three main oxidative addition mechanisms: concerted, non-polarized, and polarized. Has only one mechanism, which is the counterpart of the concerted oxidative addition.
Ligand Positioning Ligands must be in a cis position in order to undergo reductive elimination.

Oxidative addition and reductive elimination are reaction pairs that involve a change in the oxidation state and coordination number of the metal in a coordination complex.