Crystallographic and spectroscopic characterization of a nonheme Fe(IV)-O complex

Science. 2003 Feb 14;299(5609):1037-9. doi: 10.1126/science.299.5609.1037.

Abstract

Following the heme paradigm, it is often proposed that dioxygen activation by nonheme monoiron enzymes involves an iron(IV)=oxo intermediate that is responsible for the substrate oxidation step. Such a transient species has now been obtained from a synthetic complex with a nonheme macrocyclic ligand and characterized spectroscopically. Its high-resolution crystal structure reveals an iron-oxygen bond length of 1.646(3) angstroms, demonstrating that a terminal iron(IV)=oxo unit can exist in a nonporphyrin ligand environment and lending credence to proposed mechanisms of nonheme iron catalysis.

Publication types

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

MeSH terms

  • Catalysis
  • Chemical Phenomena
  • Chemistry, Physical
  • Crystallization
  • Crystallography, X-Ray
  • Iron / chemistry*
  • Ligands
  • Models, Molecular
  • Molecular Structure
  • Oxidation-Reduction
  • Oxygen / chemistry*
  • Spectrometry, Mass, Electrospray Ionization
  • Spectroscopy, Mossbauer

Substances

  • Ligands
  • ferryl iron
  • Iron
  • Oxygen