Metal ion effect on the switch of mechanism from direct oxygen transfer to metal ion-coupled electron transfer in the sulfoxidation of thioanisoles by a non-heme iron(IV)-oxo complex

J Am Chem Soc. 2011 Apr 13;133(14):5236-9. doi: 10.1021/ja200901n. Epub 2011 Mar 16.

Abstract

The mechanism of sulfoxidation of thioaniosoles by a non-heme iron(IV)-oxo complex is switched from direct oxygen transfer to metal ion-coupled electron transfer by the presence of Sc(3+). The switch in the sulfoxidation mechanism is dependent on the one-electron oxidation potentials of thioanisoles. The rate of sulfoxidation is accelerated as much as 10(2)-fold by the addition of Sc(3+).

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Electron Transport
  • Heme / chemistry
  • Iron / chemistry*
  • Organometallic Compounds / chemistry*
  • Oxygen / chemistry*
  • Safrole / analogs & derivatives*
  • Safrole / chemistry
  • Spectrophotometry, Ultraviolet
  • Sulfides / chemistry*

Substances

  • Organometallic Compounds
  • Sulfides
  • Heme
  • methylphenylsulfide
  • Iron
  • Safrole
  • Oxygen
  • sulfoxide