Trapping of a Highly Reactive Oxoiron(IV) Complex in the Catalytic Epoxidation of Olefins by Hydrogen Peroxide

Xenia Engelmann, Deesha D. Malik, Teresa Corona, Katrin Warm, Erik R. Farquhar, Marcel Swart, Wonwoo Nam, Kallol Ray

Research output: Contribution to journalArticlepeer-review

29 Scopus citations

Abstract

The generation of a nonheme oxoiron(IV) intermediate, [(cyclam)Fe IV (O)(CH 3 CN)] 2+ (2; cyclam=1,4,8,11-tetraazacyclotetradecane), is reported in the reactions of [(cyclam)Fe II ] 2+ with aqueous hydrogen peroxide (H 2 O 2 ) or a soluble iodosylbenzene (sPhIO) as a rare example of an oxoiron(IV) species that shows a preference for epoxidation over allylic oxidation in the oxidation of cyclohexene. Complex 2 is kinetically and catalytically competent to perform the epoxidation of olefins with high stereo- and regioselectivity. More importantly, 2 is likely to be the reactive intermediate involved in the catalytic epoxidation of olefins by [(cyclam)Fe II ] 2+ and H 2 O 2 . In spite of the predominance of the oxoiron(IV) cores in biology, the present study is a rare example of high-yield isolation and spectroscopic characterization of a catalytically relevant oxoiron(IV) intermediate in chemical oxidation reactions.

Original languageEnglish
Pages (from-to)4012-4016
Number of pages5
JournalAngewandte Chemie - International Edition
Volume58
Issue number12
DOIs
StatePublished - 18 Mar 2019

Keywords

  • bioinorganic chemistry
  • catalysis
  • nonheme oxoiron intermediates
  • regioselectivity
  • stereoselective epoxidation

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