Chapter 7. Olefin Epoxidation Catalyzed by Molybdenum Peroxo Complexes: A Mechanistic Study

  1. Waldemar Adam
  1. Werner R. Thiel,
  2. Michael Barz,
  3. Holger Glas and
  4. Anna-Katharina Pleier

Published Online: 30 JUN 2005

DOI: 10.1002/3527600396.ch20

Peroxide Chemistry: Mechanistic and Preparative Aspects of Oxygen Transfer

Peroxide Chemistry: Mechanistic and Preparative Aspects of Oxygen Transfer

How to Cite

Thiel, W. R., Barz, M., Glas, H. and Pleier, A.-K. (2000) Olefin Epoxidation Catalyzed by Molybdenum Peroxo Complexes: A Mechanistic Study, in Peroxide Chemistry: Mechanistic and Preparative Aspects of Oxygen Transfer (ed W. Adam), Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, FRG. doi: 10.1002/3527600396.ch20

Editor Information

  1. Institut für Organische Chemie, Universität Würzburg, Am Hubland, D-97074 Würzburg, Germany

Author Information

  1. Anorganisch-chemisches Institut, Technische Universität München, Lichtenbergstr. 4, D-85747 Garching, Germany

Publication History

  1. Published Online: 30 JUN 2005
  2. Published Print: 11 SEP 2000

ISBN Information

Print ISBN: 9783527271504

Online ISBN: 9783527600397

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Keywords:

  • olefin epoxidation;
  • molybdenum peroxo complexes;
  • oxygen transfer mechanisms;
  • proton transfer;
  • nucleophilic attack;
  • Lewis acids;
  • Brønsted acids;
  • NMR;
  • DFT;
  • ligand dissociation processes;
  • hydroperoxide activation

Summary

This chapter contains sections titled:

  • Introduction

  • Oxygen Transfer Mechanisms

  • Seven Coordinate Molybdenum Peroxo Complexes: Synthesis and Catalytic Features

  • Catalyst and Substrate in One Molecule, a First Idea on the Mechanism

  • Proton Transfer and Nucleophilic Attack: A Concerted Reaction

    • The Reaction of Lewis and Brønsted Acids with Peroxo Complexes

    • Hydrogen Bonding to Peroxo Ligands Coordinated Mo(VI)

  • A Structure/Activity Relationship for Epoxidation Catalysts

  • From Ligand Fluxionality to the Activation of the Hydroperoxide

    • A NMR and DFT Investigation on the Ligand Dissociation Processes

    • A DFT study on the Hydroperoxide Activation

  • Conclusion

  • References