Chapter 4. Substitution Reactions

  1. Prof. Ralph G. Wilkins

Published Online: 2 JUN 2003

DOI: 10.1002/3527600825.ch4

Kinetics and Mechanism of Reactions of Transition Metal Complexes, 2nd Edition

Kinetics and Mechanism of Reactions of Transition Metal Complexes, 2nd Edition

How to Cite

Wilkins, R. G. (1991) Substitution Reactions, in Kinetics and Mechanism of Reactions of Transition Metal Complexes, 2nd Edition, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, FRG. doi: 10.1002/3527600825.ch4

Author Information

  1. University of Warwick, Dept. of Chemistry, Coventry CV4 7AL, Great Britain

Publication History

  1. Published Online: 2 JUN 2003
  2. Published Print: 27 AUG 1991

ISBN Information

Print ISBN: 9783527282531

Online ISBN: 9783527600823

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Keywords:

  • substitution;
  • octahedral complexes;
  • metal ions;
  • unidentate ligands;
  • outer sphere complexes;
  • removal;
  • multidentate ligands;
  • chelates;
  • dechelation;
  • macrocycles;
  • azamacrocycles;
  • crown-ethers;
  • cryptands;
  • porphyrins;
  • square-planar complexes;
  • tetrahedral complexes;
  • metalloproteins

Summary

This chapter contains sections titled:

  • The Characteristics of Substitution Reactions

    • Solvated Metal Ions

    • Representation of Substitution Mechanisms

  • Substitution in Octahedral Complexes

    • Solvent Exchange with Metal Ions

    • The Interchange of Different Unidentate Ligands

    • Outer Sphere Complexes

    • Characteristics of the Various Mechanisms

    • The Limiting First-Order Rate Constant

    • Second-Order Rate Constants

    • Summary

  • Accelerated Substitution of Unidentate Ligands

    • H+-Assisted Removal

    • Metal Ion-Assisted Removal

    • Ligand-Assisted Removal

    • Base-Assisted Removal

    • The Quest for Five Coordinate Intermediates

  • Replacement Reactions Involving Multidentate Ligands

    • The Formation of Chelates

    • Effect of [H+] on the Rates of Substitution in Chelate Complexes

    • Metal Ion-Assisted Dechelation

    • Ligand-Assisted Dechelation

  • Replacement Reactions Involving Macrocycles

    • Azamacrocycles

    • Crown-Ethers and Cryptands

    • Porphyrins

  • Substitution in Square-Planar Complexes

    • The Kinetics of Replacement Involving Unidentate Ligands

    • Activation Parameters

  • Ligand Effects on the Rate

    • Effect of Entering Ligand

    • Effect of Leaving Group

    • Effect of Ligands Already Present

    • Effect of Solvent

    • Reaction Pathways

    • Chelation in Square-Planar Complexes

  • Substitution in Tetrahedral Complexes

  • Substitution in Five-Coordinate Complexes

  • Substitution in Organized Surfactant Systems

  • Substitution in Metalloproteins