title: Light-driven, proton-controlled, catalytic aerobic C-H oxidation mediated by a Mn(III) porphyrinoid complex.
abstract: The visible light-driven, catalytic aerobic oxidation of benzylic C-H bonds was mediated by a Mn(III) 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 [Mn(III)(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 Mn(V)(O) complex is also protonated at the same remote site at -60 °C, but undergoes valence tautomerization upon warming.
authors.affiliation: †Department of Chemistry, The Johns Hopkins University, Baltimore, Maryland 21218, United States.
authors.forename: Heather M
authors.initials: HM
authors.lastname: Neu
authors.affiliation: ‡Department of Material and Life Science, Graduate School of Engineering, Osaka University, ALCA, Japan Science and Technology Agency, Suita, Osaka 565-0871, Japan.
authors.forename: Jieun
authors.initials: J
authors.lastname: Jung
authors.affiliation: †Department of Chemistry, The Johns Hopkins University, Baltimore, Maryland 21218, United States.
authors.forename: Regina A
authors.initials: RA
authors.lastname: Baglia
authors.affiliation: †Department of Chemistry, The Johns Hopkins University, Baltimore, Maryland 21218, United States.
authors.forename: Maxime A
authors.initials: MA
authors.lastname: Siegler
authors.affiliation: ‡Department of Material and Life Science, Graduate School of Engineering, Osaka University, ALCA, Japan Science and Technology Agency, Suita, Osaka 565-0871, Japan.
authors.forename: Kei
authors.initials: K
authors.lastname: Ohkubo
authors.affiliation: ‡Department of Material and Life Science, Graduate School of Engineering, Osaka University, ALCA, Japan Science and Technology Agency, Suita, Osaka 565-0871, Japan.|§Department of Bioinspired Science, Ewha Womans University, Seoul 120-750, Korea.
authors.forename: Shunichi
authors.initials: S
authors.lastname: Fukuzumi
authors.affiliation: †Department of Chemistry, The Johns Hopkins University, Baltimore, Maryland 21218, United States.
authors.forename: David P
authors.initials: DP
authors.lastname: Goldberg
mesh_terms: D002244:Carbon / Q000737:chemistry*; D002384:Catalysis; D006859:Hydrogen / Q000737:chemistry*; D007700:Kinetics; D008024:Ligands; D008027:Light; D008345:Manganese / Q000737:chemistry*; D008665:Metalloporphyrins / Q000737:chemistry*; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry*; D011522:Protons
chemical_list: D008024:Ligands; D008665:Metalloporphyrins; D011522:Protons; D008345:Manganese; D002244:Carbon; D006859:Hydrogen; D010100:Oxygen
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