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Angew Chem Int Ed Engl. 2018 Mar 12;57(12):3207-3211. doi: 10.1002/anie.201712678. Epub 2018 Feb 19.

A Non-Heme Iron Photocatalyst for Light-Driven Aerobic Oxidation of Methanol.

Author information

1
Molecular Inorganic Chemistry, Stratingh Institute for Chemistry, Faculty of Science and Engineering, University of Groningen, Nijenborgh 4, 9747AG, Groningen, The Netherlands.
2
Faculty of Chemistry, University of Belgrade, Studentski trg 12-16, 11000, Belgrade, Serbia.
3
Department of Chemistry and Center for Metals in Biocatalysis, University of Minnesota, 207 Pleasant Street SE, Minneapolis, MN, 55455, USA.

Abstract

Non-heme (L)FeIII and (L)FeIII -O-FeIII (L) complexes (L=1,1-di(pyridin-2-yl)-N,N-bis(pyridin-2-ylmethyl)ethan-1-amine) underwent reduction under irradiation to the FeII state with concomitant oxidation of methanol to methanal, without the need for a secondary photosensitizer. Spectroscopic and DFT studies support a mechanism in which irradiation results in charge-transfer excitation of a FeIII -μ-O-FeIII complex to generate [(L)FeIV =O]2+ (observed transiently during irradiation in acetonitrile), and an equivalent of (L)FeII . Under aerobic conditions, irradiation accelerates reoxidation from the FeII to the FeIII state with O2 , thus closing the cycle of methanol oxidation to methanal.

KEYWORDS:

diiron complexes; iron; oxidation; photochemistry; reaction mechanisms

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