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

Juan Chen, Stepan Stepanovic, Apparao Draksharapu, Maja Gruden, Wesley R. Browne

Research output: Contribution to journalArticlepeer-review

11 Scopus citations

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.

Original languageEnglish (US)
Pages (from-to)3207-3211
Number of pages5
JournalAngewandte Chemie - International Edition
Volume57
Issue number12
DOIs
StatePublished - Mar 12 2018

Bibliographical note

Funding Information:
The COST association action CM1305 ECOSTBio (STSM grant 38503), the European Research Council (ERC 279549, WRB), Labex ARCANE (ANR-11-LABX-003), the Serbian Ministry of Science (OI172035), and the Chinese Scholarship Council (CSC) are acknowledged for financial support. We thank the Center for Information Technology of the University of Groningen for their support and for providing access to the Peregrine high-performance computing cluster. We thank Prof. Edwin Otten for X-ray structural analysis of 3, and Dr. Carole Duboc and Dr. Sandeep Padamati for recording X-band EPR spectra of 3 at 4 K.

Publisher Copyright:
© 2018 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Keywords

  • diiron complexes
  • iron
  • oxidation
  • photochemistry
  • reaction mechanisms

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