Oxidation of cyclohexane by a high-valent iron bispidine complex: a combined experimental and computational mechanistic study

J Phys Chem A. 2008 Dec 18;112(50):13028-36. doi: 10.1021/jp8037895.

Abstract

Experimental data suggest that there are various competing pathways for the catalytic and stoichiometric oxygenation of cyclohexane, assisted by iron-bispidine complexes and using various oxidants (H(2)O(2), O(2), PhIO). Density functional theory calculations indicate that both Fe(IV)=O and Fe(V)=O species are accessible and efficiently transfer their oxygen atoms to cyclohexane. The reactivities of the two isomers each and the two possible spin states for the Fe(IV)=O and Fe(V)=O species are sufficiently different to allow an interpretation of the experimental data.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Bridged Bicyclo Compounds, Heterocyclic / chemistry*
  • Cyclohexanes / chemistry*
  • Cyclohexanes / metabolism
  • Hydrogen Peroxide / chemistry
  • Hydroxylation
  • Iron / chemistry*
  • Models, Molecular
  • Molecular Conformation
  • Molecular Structure
  • Oxidants / chemistry
  • Oxidation-Reduction
  • Oxygen / chemistry

Substances

  • Bridged Bicyclo Compounds, Heterocyclic
  • Cyclohexanes
  • Oxidants
  • bispidine
  • Cyclohexane
  • Hydrogen Peroxide
  • Iron
  • Oxygen