Status of reactive non-heme metal-oxygen intermediates in chemical and enzymatic reactions

J Am Chem Soc. 2014 Oct 8;136(40):13942-58. doi: 10.1021/ja507807v. Epub 2014 Sep 29.

Abstract

Selective functionalization of unactivated C-H bonds, water oxidation, and dioxygen reduction are extremely important reactions in the context of finding energy carriers and conversion processes that are alternatives to the current fossil-based oil for energy. A range of metalloenzymes achieve these challenging tasks in biology by using cheap and abundant transition metals, such as iron, copper, and manganese. High-valent metal-oxo and metal-dioxygen (superoxo, peroxo, and hydroperoxo) cores act as active intermediates in many of these processes. The generation of well-described model compounds can provide vital insights into the mechanisms of such enzymatic reactions. This perspective provides a focused rather than comprehensive review of the recent advances in the chemistry of biomimetic high-valent metal-oxo and metal-dioxygen complexes, which can be related to our understanding of the biological systems.

Publication types

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

MeSH terms

  • Biomimetics
  • Enzymes / metabolism*
  • Metals / chemistry*
  • Metals / metabolism*
  • Oxygen / chemistry*
  • Oxygen / metabolism*

Substances

  • Enzymes
  • Metals
  • Oxygen