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

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

doi:10.1021/jacs.5b00816

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

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

Department of Chemistry & Nanoscience

Research output: Contribution to journal › Article › peer-review

55 Scopus citations

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.

Original language	English
Pages (from-to)	4614-4617
Number of pages	4
Journal	Journal of the American Chemical Society
Volume	137
Issue number	14
DOIs	https://doi.org/10.1021/jacs.5b00816
State	Published - 15 Apr 2015

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© 2015 American Chemical Society.

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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 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.",

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AU - Neu, Heather M.

AU - Jung, Jieun

AU - Baglia, Regina A.

AU - Siegler, Maxime A.

AU - Ohkubo, Kei

AU - Fukuzumi, Shunichi

AU - Goldberg, David P.

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AB - 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.

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

Abstract

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