Fe(TPA)-catalyzed alkane hydroxylation can be a metal-based oxidation

Jinheung Kim, Cheal Kim, Roger G. Harrison, Elizabeth C. Wilkinson, Lawrence Que

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25 Scopus citations


The hydroxylation of cyclohexane by t-butyl hydroperoxide using [Fe2O(TPA)2(H2O)2]4+ (1, TPA=tris(2-pyridylmethyl)amine) as the catalyst has been investigated with the use of a syringe pump to control the concentration of the alkyl hydroperoxide. Unlike an alkoxy radical-based radical chain autoxidation mechanism, the reaction observed produces only alcohol (no ketone) with a deuterium kinetic isotope effect of 10, similar to heme catalyzed hydroxylations. An alkylperoxoiron(III) intermediate can be trapped at -40°C and characterized by a number of spectroscopic methods. A mechanistic scheme is proposed involving this intermediate which either serves as the precursor to the metal-based oxidant or oxidizes the substrate directly.

Original languageEnglish
Pages (from-to)83-89
Number of pages7
JournalJournal of Molecular Catalysis A: Chemical
Issue number1-3
StatePublished - 14 Mar 1997

Bibliographical note

Funding Information:
This work was supported by funds from the National Institutes of Health (Grant No. GM-38767).


  • Alkylperoxide intermediates
  • Nonheme iron complexes
  • Oxygen activation


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