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

被引：41

作者：

Hong, Young Hyun ^{[1
]}

Han, Ji Won ^{[1
]}

Jung, Jieun ^{[1
,2
]}

Nakagawa, Tatsuo ^{[3
]}

Lee, Yong-Min ^{[1
]}

Nam, Wonwoo ^{[1
,4
]}

Fukuzumi, Shunichi ^{[1
,5
]}

机构：

[1] Ewha Womans Univ, Dept Chem & Nano Sci, Seoul 03760, South Korea

[2] Nagoya Univ, Grad Sch Sci, Dept Chem, Chikusa Ku, Nagoya, Aichi 4648602, Japan

[3] Japan Sci & Technol Agcy JST, Unisoku Co Ltd, SENTAN, Hirakata, Osaka 5730131, Japan

[4] Shaanxi Normal Univ, Sch Chem & Chem Engn, Xian 710119, Shaanxi, Peoples R China

[5] Meijo Univ, Japan Sci & Technol Agcy JST, Fac Sci & Engn, SENTAN, Nagoya, Aichi 4688502, Japan

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2019年 / 141卷 / 23期

关键词：

ELECTRON-TRANSFER; HIGHLY EFFICIENT; PHOTOSYSTEM-II; SUPEROXIDE ION; OXIDATION; MECHANISMS; DISPROPORTIONATION; BENZENE; SULFIDE; ALKENES;

D O I：

10.1021/jacs.9b02864

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Photocatalytic oxygenation of hexamethylbenzene occurs under visible-light irradiation of an O(2)(-)saturated acetonitrile solution containing a cobalt porphyrin complex Co-II(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 O-2 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 O-18-labeling experiments with (H2O)-O-18 and O-18(2). 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 O-2 as a two-electron oxidant.

引用

页码：9155 / 9159

页数：5

共 45 条

[1] OXIDATION OF THE CYCLOHEXADIENYL RADICAL BY METAL-IONS - PULSE-RADIOLYSIS STUDY [J].