TY - JOUR
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
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.
UR - http://www.scopus.com/inward/record.url?scp=85067363053&partnerID=8YFLogxK
U2 - 10.1021/jacs.9b02864
DO - 10.1021/jacs.9b02864
M3 - Article
C2 - 31145595
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 -