Iron-oxidation-state-dependent O-O bond cleavage of meta-chloroperbenzoic acid to form an iron(IV)-oxo complex

Kallol Ray, Sang Mok Lee, Lawrence Que

Research output: Contribution to journalArticlepeer-review

26 Scopus citations

Abstract

The mechanism of formation of [FeIV(O)(N4Py)]2+ (2, N4Py = N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine) from the reaction of [FeII(N4Py)(CH3CN)]2+ (1) with m-chloroperbenzoic acid (mCPBA) in CH2Cl2 at -30 °C has been studied on the basis of the visible spectral changes observed and the reaction stoichiometry. It is shown that the conversion of 1 to 2 in 90% yield requires 1.5 equiv. peracid and takes place in two successive one-electron steps via an [FeIII(N4Py)OH]2+(3) intermediate. The first oxidation step uses 0.5 equiv. peracid and produces 0.5 equiv. 3-chlorobenzoic acid, while the second step uses 1 equiv. peracid and affords byproducts derived from chlorophenyl radical. We conclude that the FeII(N4Py) center promotes O-O bond heterolysis, while the FeIII(N4Py) center favors O-O bond homolysis, so the nature of O-O bond cleavage is dependent on the iron oxidation state.

Original languageEnglish (US)
Pages (from-to)1066-1069
Number of pages4
JournalInorganica Chimica Acta
Volume361
Issue number4
DOIs
StatePublished - Mar 3 2008

Bibliographical note

Funding Information:
This work was supported by the National Institutes of Health (Grant GM-33162).

Keywords

  • Iron oxidation state
  • Non-heme ligands
  • O-O bond lysis
  • Oxoiron(IV) complexes

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