Formation of a room temperature stable Fe(V)(O) complex: reactivity toward unactivated C-H bonds

J Am Chem Soc. 2014 Jul 9;136(27):9524-7. doi: 10.1021/ja412537m. Epub 2014 Jan 16.

Abstract

An Fe(V)(O) complex has been synthesized from equimolar solutions of (Et4N)2[Fe(III)(Cl)(biuret-amide)] and mCPBA in CH3CN at room temperature. The Fe(V)(O) complex has been characterized by UV-vis, EPR, Mössbauer, and HRMS and shown to be capable of oxidizing a series of alkanes having C-H bond dissociation energies ranging from 99.3 kcal mol(-1) (cyclohexane) to 84.5 kcal mol(-1) (cumene). Linearity in the Bell-Evans-Polayni graph and the finding of a large kinetic isotope effect suggest that hydrogen abstraction is engaged the rate-determining step.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Iron Compounds / chemical synthesis*
  • Iron Compounds / chemistry
  • Molecular Structure
  • Oxygen / chemistry*
  • Temperature*

Substances

  • Iron Compounds
  • Oxygen