H2O2 activation with biomimetic non-haem iron complexes and AcOH: connecting the g = 2.7 EPR signal with a visible chromophore

Olga V. Makhlynets; Williamson N. Oloo; Yurii S. Moroz; Irina G. Belaya; Taryn D. Palluccio; Alexander S. Filatov; Peter Müller; Matthew A. Cranswick; Lawrence Que; Elena V. Rybak-Akimova

doi:10.1039/C3CC47632D

H₂O₂ activation with biomimetic non-haem iron complexes and AcOH: connecting the g = 2.7 EPR signal with a visible chromophore†

Olga V. Makhlynets,^a Williamson N. Oloo,^b Yurii S. Moroz,^a Irina G. Belaya,^a Taryn D. Palluccio,^a Alexander S. Filatov,^c Peter Müller,^d Matthew A. Cranswick,^b Lawrence Que, Jr.*^b and Elena V. Rybak-Akimova*^a

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^a Department of Chemistry, Tufts University, 62 Talbot Avenue, Medford, Massachusetts 02155, USA
E-mail: erybakak@tufts.edu
Fax: +1-6176273443
Tel: +1-6176273413

^b Department of Chemistry and Center for Metals in Biocatalysis, University of Minnesota, 207 Pleasant Street S.E., Minneapolis, USA

^c Department of Chemistry, University at Albany, 1400 Washington Avenue, Albany, New York 12222, USA

^d Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Ave, Cambridge, USA

Abstract

Mechanistic studies of H₂O₂ activation by complexes related to [(BPMEN)Fe^II(CH₃CN)₂]²⁺ with electron-rich pyridines revealed that a new intermediate formed in the presence of acetic acid with a 465 nm visible band can be associated with an unusual g = 2.7 EPR signal. We postulate that this chromophore is an acylperoxoiron(III) intermediate.

This article is part of the themed collection: Biological oxidation reactions: mechanisms and design of new catalysts

Chemical Communications

H₂O₂ activation with biomimetic non-haem iron complexes and AcOH: connecting the g = 2.7 EPR signal with a visible chromophore†

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H₂O₂ activation with biomimetic non-haem iron complexes and AcOH: connecting the g = 2.7 EPR signal with a visible chromophore

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