Mechanism of water oxidation by single-site ruthenium complex catalysts

J Am Chem Soc. 2010 Feb 10;132(5):1545-57. doi: 10.1021/ja904906v.

Abstract

The mechanism of Ce(IV) water oxidation catalyzed by [Ru(tpy)(bpm)(OH(2))](2+) (tpy = 2,2':6',2''-terpyridine; bpm = 2,2'-bipyrimidine) and related single-site catalysts has been determined by a combination of mixing and stopped-flow experiments with spectrophotometric monitoring. The mechanism features O---O coupling by water attack on Ru(V)=O(3+) and three peroxidic intermediates that have been characterized by a combination of spectroscopy and DFT calculations.

Publication types

  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Catalysis
  • Models, Molecular
  • Molecular Structure
  • Oxidation-Reduction
  • Oxygen / chemistry
  • Ruthenium Compounds / chemistry*
  • Spectrophotometry
  • Water / chemistry*

Substances

  • Ruthenium Compounds
  • Water
  • Oxygen