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

46 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

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© 2019 American Chemical Society.

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@article{021d9588b9a8426b936b7dd18704b515,

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",

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year = "2019",

month = jun,

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doi = "10.1021/jacs.9b02864",

language = "English",

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journal = "Journal of the American Chemical Society",

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T1 - Photocatalytic Oxygenation Reactions with a Cobalt Porphyrin Complex Using Water as an Oxygen Source and Dioxygen as an Oxidant

AU - Hong, Young Hyun

AU - Han, Ji Won

AU - Jung, Jieun

AU - Nakagawa, Tatsuo

AU - Lee, Yong Min

AU - Nam, Wonwoo

AU - Fukuzumi, Shunichi

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.

UR - https://www.scopus.com/pages/publications/85067363053

U2 - 10.1021/jacs.9b02864

DO - 10.1021/jacs.9b02864

M3 - Article

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AN - SCOPUS:85067363053

SN - 0002-7863

VL - 141

SP - 9155

EP - 9159

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 23

ER -

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

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