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Updated: May 24, 2025

Light-driven Enzymatic Decarboxylation
Published on: May 22, 2016
Bio-inspired oxidation catalysis based on proton-coupled electron transfer: Toward efficient and selective oxidation
1Department of Chemistry, Faculty of Pure and Applied Sciences, University of Tsukuba, 1-1-1 Tennoudai, Tsukuba, Ibaraki 305-8571, Japan.
Abstract:
In this paper, a trail of my research is described starting from oxidation of alkanes by FeIII-TPA (TPA = tris(2-pyridylmethyl)amine) complexes with alkyl hydroperoxides to Ru-pyridylamine complexes which can be converted to RuIV-oxo complexes in different spin states (S = 1 or 0) through proton-coupled electron-transfer oxidation of the corresponding RuII-aqua complexes, clarifying that those spin states do not affect the reactivity in water. The introduction of strongly donating N-heterocyclic carbene (NHC) moiety allows us to create a RuIII-oxyl complex showing different reactivity from that of RuIV-oxo complexes. Manipulation of second coordination spheres (SCSs) of Ru-TPA complexes is also described, visualizing unique functionality. The introduction of hydrophobic SCS to a FeII-NHC complex enables to catalyze selective oxidation of methane to form methanol in high selectivity in aqueous media based on the "catch-and-release" strategy, which can also allow us to achieve highly selective two-electron oxidation of aromatic compounds.
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