A Non‐Heme Iron Photocatalyst for Light‐Driven Aerobic Oxidation of Methanol |
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| Authors: | Juan Chen Stepan Stepanovic Dr Apparao Draksharapu Prof?Dr Maja Gruden Prof?Dr Wesley R Browne |
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| Affiliation: | 1. Molecular Inorganic Chemistry, Stratingh Institute for Chemistry, Faculty of Science and Engineering, University of Groningen, Groningen, The Netherlands;2. Faculty of Chemistry, University of Belgrade, Belgrade, Serbia;3. Department of Chemistry and Center for Metals in Biocatalysis, University of Minnesota, Minneapolis, MN, USA |
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| 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. |
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| Keywords: | diiron complexes iron oxidation photochemistry reaction mechanisms |
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