Photocatalytic Oxygenation Reactions with a Cobalt Porphyrin Complex Using Water as an Oxygen Source and Dioxygen as an Oxidant

Young Hyun Hong; Ji Won Han; Jieun Jung; Tatsuo Nakagawa; Yong Min Lee; Wonwoo Nam; Shunichi Fukuzumi

doi:10.1021/jacs.9b02864

Photocatalytic Oxygenation Reactions with a Cobalt Porphyrin Complex Using Water as an Oxygen Source and Dioxygen as an Oxidant

Young Hyun Hong, Ji Won Han, Jieun Jung, Tatsuo Nakagawa, Yong Min Lee, Wonwoo Nam, Shunichi Fukuzumi

Department of Chemistry & Nanoscience

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

43 Scopus citations

Abstract

Photocatalytic oxygenation of hexamethylbenzene occurs under visible-light irradiation of an O₂-saturated acetonitrile solution containing a cobalt porphyrin complex Co^II(TPP) (TPP^2- = tetraphenylporphyrin dianion), water, and triflic acid (HOTf) via a one-photon-two-electron process, affording pentamethylbenzyl alcohol and hydrogen peroxide as products with a turnover number of >6000; in this reaction, H₂O and O₂ were used as an oxygen source and a two-electron oxidant, respectively. The photocatalytic mechanism was clarified by means of electron paramagnetic resonance, time-resolved fluorescence, and transient absorption measurements as well as ¹⁸O-labeling experiments with H₂¹⁸O and ¹⁸O₂. To the best of our knowledge, we report the first example of efficient photocatalytic oxygenation of an organic substrate by a metal complex using H₂O as an oxygen source and O₂ as a two-electron oxidant.

Original language	English
Pages (from-to)	9155-9159
Number of pages	5
Journal	Journal of the American Chemical Society
Volume	141
Issue number	23
DOIs	https://doi.org/10.1021/jacs.9b02864
State	Published - 12 Jun 2019

Bibliographical note

Funding Information:
This work was supported by the NRF of Korea through CRI (NRF-2012R1A3A2048842 to W.N.) and the Basic Science Research Program (2017R1D1A1B03029982 to Y.-M.L. and 2017R1D1A1B03032615 to S.F.) and by MEXT (Grant-in-Aid 16H02268 to S.F.). We appreciate Dr. Muniyandi Sankar-alingam for help with EPR measurements.

Publisher Copyright:
© 2019 American Chemical Society.

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title = "Photocatalytic Oxygenation Reactions with a Cobalt Porphyrin Complex Using Water as an Oxygen Source and Dioxygen as an Oxidant",

abstract = "Photocatalytic oxygenation of hexamethylbenzene occurs under visible-light irradiation of an O2-saturated acetonitrile solution containing a cobalt porphyrin complex CoII(TPP) (TPP2- = tetraphenylporphyrin dianion), water, and triflic acid (HOTf) via a one-photon-two-electron process, affording pentamethylbenzyl alcohol and hydrogen peroxide as products with a turnover number of >6000; in this reaction, H2O and O2 were used as an oxygen source and a two-electron oxidant, respectively. The photocatalytic mechanism was clarified by means of electron paramagnetic resonance, time-resolved fluorescence, and transient absorption measurements as well as 18O-labeling experiments with H218O and 18O2. To the best of our knowledge, we report the first example of efficient photocatalytic oxygenation of an organic substrate by a metal complex using H2O as an oxygen source and O2 as a two-electron oxidant.",

author = "Hong, {Young Hyun} and Han, {Ji Won} and Jieun Jung and Tatsuo Nakagawa and Lee, {Yong Min} and Wonwoo Nam and Shunichi Fukuzumi",

note = "Funding Information: This work was supported by the NRF of Korea through CRI (NRF-2012R1A3A2048842 to W.N.) and the Basic Science Research Program (2017R1D1A1B03029982 to Y.-M.L. and 2017R1D1A1B03032615 to S.F.) and by MEXT (Grant-in-Aid 16H02268 to S.F.). We appreciate Dr. Muniyandi Sankar-alingam for help with EPR measurements. Publisher Copyright: {\textcopyright} 2019 American Chemical Society.",

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AU - Nakagawa, Tatsuo

AU - Lee, Yong Min

AU - Nam, Wonwoo

AU - Fukuzumi, Shunichi

N1 - Funding Information: This work was supported by the NRF of Korea through CRI (NRF-2012R1A3A2048842 to W.N.) and the Basic Science Research Program (2017R1D1A1B03029982 to Y.-M.L. and 2017R1D1A1B03032615 to S.F.) and by MEXT (Grant-in-Aid 16H02268 to S.F.). We appreciate Dr. Muniyandi Sankar-alingam for help with EPR measurements. Publisher Copyright: © 2019 American Chemical Society.

PY - 2019/6/12

Y1 - 2019/6/12

N2 - Photocatalytic oxygenation of hexamethylbenzene occurs under visible-light irradiation of an O2-saturated acetonitrile solution containing a cobalt porphyrin complex CoII(TPP) (TPP2- = tetraphenylporphyrin dianion), water, and triflic acid (HOTf) via a one-photon-two-electron process, affording pentamethylbenzyl alcohol and hydrogen peroxide as products with a turnover number of >6000; in this reaction, H2O and O2 were used as an oxygen source and a two-electron oxidant, respectively. The photocatalytic mechanism was clarified by means of electron paramagnetic resonance, time-resolved fluorescence, and transient absorption measurements as well as 18O-labeling experiments with H218O and 18O2. To the best of our knowledge, we report the first example of efficient photocatalytic oxygenation of an organic substrate by a metal complex using H2O as an oxygen source and O2 as a two-electron oxidant.

AB - Photocatalytic oxygenation of hexamethylbenzene occurs under visible-light irradiation of an O2-saturated acetonitrile solution containing a cobalt porphyrin complex CoII(TPP) (TPP2- = tetraphenylporphyrin dianion), water, and triflic acid (HOTf) via a one-photon-two-electron process, affording pentamethylbenzyl alcohol and hydrogen peroxide as products with a turnover number of >6000; in this reaction, H2O and O2 were used as an oxygen source and a two-electron oxidant, respectively. The photocatalytic mechanism was clarified by means of electron paramagnetic resonance, time-resolved fluorescence, and transient absorption measurements as well as 18O-labeling experiments with H218O and 18O2. To the best of our knowledge, we report the first example of efficient photocatalytic oxygenation of an organic substrate by a metal complex using H2O as an oxygen source and O2 as a two-electron oxidant.

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Photocatalytic Oxygenation Reactions with a Cobalt Porphyrin Complex Using Water as an Oxygen Source and Dioxygen as an Oxidant

Abstract

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