A highly reactive mononuclear non-heme manganese(IV)-oxo complex that can activate the strong C-H bonds of alkanes

J Am Chem Soc. 2011 Dec 21;133(50):20088-91. doi: 10.1021/ja208523u. Epub 2011 Nov 29.

Abstract

A mononuclear non-heme manganese(IV)-oxo complex has been synthesized and characterized using various spectroscopic methods. The Mn(IV)-oxo complex shows high reactivity in oxidation reactions, such as C-H bond activation, oxidations of olefins, alcohols, sulfides, and aromatic compounds, and N-dealkylation. In C-H bond activation, the Mn(IV)-oxo complex can activate C-H bonds as strong as those in cyclohexane. It is proposed that C-H bond activation by the non-heme Mn(IV)-oxo complex does not occur via an oxygen-rebound mechanism. The electrophilic character of the non-heme Mn(IV)-oxo complex is demonstrated by a large negative ρ value of -4.4 in the oxidation of para-substituted thioanisoles.

Publication types

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

MeSH terms

  • Alkanes / chemistry*
  • Heme / chemistry
  • Manganese / chemistry*
  • Models, Molecular
  • Oxidation-Reduction
  • Oxygen / chemistry*
  • Spectrophotometry, Ultraviolet
  • X-Ray Absorption Spectroscopy

Substances

  • Alkanes
  • Heme
  • Manganese
  • Oxygen