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Light-Driven, Proton-Controlled, Catalytic Aerobic C–H Oxidation Mediated by a Mn(III) Porphyrinoid Complex

2015; American Chemical Society; Volume: 137; Issue: 14 Linguagem: Inglês

10.1021/jacs.5b00816

1943-2984

Heather M. Neu, Jieun Jung, Regina A. Baglia, Maxime A. Siegler, Kei Ohkubo, Shunichi Fukuzumi, David P. Goldberg,

Oxidative Organic Chemistry Reactions

The visible light-driven, catalytic aerobic oxidation of benzylic C–H bonds was mediated by a MnIII corrolazine complex. To achieve catalytic turnovers, a strict selective requirement for the addition of protons was established. The resting state of the catalyst was unambiguously characterized by X-ray diffraction as [MnIII(H2O)(TBP8Cz(H))]+, in which a single, remote site on the ligand is protonated. If two remote sites are protonated, however, reactivity with O2 is shut down. Spectroscopic methods revealed that the related MnV(O) complex is also protonated at the same remote site at −60 °C, but undergoes valence tautomerization upon warming.