Catalytically Active Iron(IV)oxo Species Based on a Bis(pyridinyl)phenanthrolinylmethane

Hüppe, H.M. and Keisers, K. and Fink, F. and Mürtz, S.D. and Hoffmann, A. and Iffland, L. and Apfel, U.-P. and Herres-Pawlis, S.

Volume: 60 Pages: 987-998
DOI: 10.1002/ijch.202000009
Published: 2020

Starting from the mononuclear iron(II) complex [Fe(MeCPy2Phen)(MeCN)2]2+, a non-heme Fe(IV)oxo complex [FeIV(MeCPy2Phen)O]2+ was synthesized via oxidation with meta-chloroperoxybenzoic acid (mCPBA). The Fe(IV)oxo complex was characterized using UV/Vis spectroscopy, Mößbauer spectroscopy and CSI mass spectrometry. The ability of this species to oxidize C−H bonds was tested with cyclohexane and adamantane as model substrates. For cyclohexane, an alcohol-to-ketone ratio (A/K) of 6.1 and efficiencies up to 55 were obtained. In case of adamantane, the ratio of tertiary over secondary products (3°/2°) is 38. In combination, this indicates the iron(IV)oxo complex being the catalytically active species. © 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA

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