Electronic design criteria for O-O bond formation via metal-oxo complexes

Inorg Chem. 2008 Mar 17;47(6):1849-61. doi: 10.1021/ic701972n.

Abstract

Metal-oxos are critical intermediates for the management of oxygen and its activation. The reactivity of the metal-oxo is central to the formation of O-O bonds, which is the essential step for oxygen generation. Two basic strategies for the formation of O-O bonds at metal-oxo active sites are presented. The acid-base (AB) strategy involves the attack of a nucleophilic oxygen species (e.g., hydroxide) on an electrophilic metal-oxo. Here, active-site designs must incorporate the assembly of a hydroxide (or water) proximate to a high-valent metal-oxo of even d electron count. For the radical coupling (RC) strategy, two high-valent metal-oxos of an odd d electron count are needed to drive O-O coupling. This Forum Article focuses on the different electronic structures of terminal metal-oxos that support AB and RC strategies and the design of ligand scaffolds that engender these electronic structures.

Publication types

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

MeSH terms

  • Binding Sites
  • Hydroxides / chemistry
  • Kinetics
  • Metals / chemistry*
  • Models, Molecular
  • Oxygen / chemistry*
  • Oxygen / metabolism
  • Water / chemistry

Substances

  • Hydroxides
  • Metals
  • Water
  • Oxygen