5. Water Oxidation by Ruthenium Catalysts with Non-Innocent Ligands

  1. Antoni Llobet
  1. Tohru Wada1,
  2. Koji Tanaka2,
  3. James T. Muckerman3 and
  4. Etsuko Fujita3

Published Online: 18 APR 2014

DOI: 10.1002/9781118698648.ch5

Molecular Water Oxidation Catalysis: A Key Topic for New Sustainable Energy Conversion Schemes

Molecular Water Oxidation Catalysis: A Key Topic for New Sustainable Energy Conversion Schemes

How to Cite

Wada, T., Tanaka, K., Muckerman, J. T. and Fujita, E. (2014) Water Oxidation by Ruthenium Catalysts with Non-Innocent Ligands, in Molecular Water Oxidation Catalysis: A Key Topic for New Sustainable Energy Conversion Schemes (ed A. Llobet), John Wiley & Sons, Ltd, Chichester, UK. doi: 10.1002/9781118698648.ch5

Editor Information

  1. Institute of Chemical Research of Catalonia, Tarragona, Spain

Author Information

  1. 1

    Department of Chemistry, College of Science and Research Center for Smart Molecules, Rikkyo University, Toshima, Tokyo, Japan

  2. 2

    Institute for Integrated Cell-Material Sciences, Kyoto University, Kyoto, Japan

  3. 3

    Chemistry Department, Brookhaven National Laboratory, Upton, NY, USA

Publication History

  1. Published Online: 18 APR 2014
  2. Published Print: 16 MAY 2014

ISBN Information

Print ISBN: 9781118413371

Online ISBN: 9781118698648

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Keywords:

  • dinuclear Ru complexes;
  • dioxolene ligand;
  • intramolecular o–o coupling;
  • mononuclear Ru–aqua complexes;
  • non-innocent ligands (NILs);
  • ruthenium (Ru) catalysts;
  • Tanaka catalyst;
  • water oxidation

Summary

The possible reaction path for O–O bond formation has been a point of contention among investigators of water oxidation, but there is a growing consensus acknowledging two main pathways: (1) a nucleophilic attack of water on a high-valent metal–oxo species, and (2) a coupling reaction of two metal–oxo species to give μ -peroxide intermediates. This chapter summarizes the novel features of the dinuclear and related mononuclear Ruthenium (Ru) species with quinone ligands. It also summarizes the comparison of their properties with those of the Ru analogs in which the bpy ligand replaces quinone. The chapter explains electrochemical water oxidation using the Tanaka catalyst. It further discusses the acid–base equilibrium and redox behavior of mononuclear Ru–aqua complexes with a variety of dioxolene ligands. The more complicated redox and catalytic properties of the Tanaka catalyst and its related dinuclear complexes are explained.