Remarkable Acid Catalysis in Proton-Coupled Electron-Transfer Reactions of a Chromium(III)-Superoxo Complex

被引：26

作者：

Devi, Tarali ^{[1
]}

Lee, Yong-Min ^{[1
]}

Nam, Wonwoo ^{[1
,2
]}

Fukuzumi, Shunichi ^{[1
,3
]}

机构：

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

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

[3] Meijo Univ, Fac Sci & Engn, Nagoya, Aichi 4688502, Japan

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2018年 / 140卷 / 27期

关键词：

MONONUCLEAR NONHEME IRON; CONTAINING SUPEROXIDE-DISMUTASE; SMALL-MOLECULE ACTIVATION; H BOND-CLEAVAGE; C-H; ATOM TRANSFER; SPECTROSCOPIC CHARACTERIZATION; IRON(III)-SUPEROXO COMPLEX; IRON(IV)-OXO COMPLEX; OXIDATION REACTIONS;

D O I：

10.1021/jacs.8b02303

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Much enhanced acid catalysis was observed in oxygen atom transfer (OAT) reactions by a mononuclear nonheme Cr(III)-superoxo complex, [(Cl)-(TMC)Cr-III(O-2)](+) (1), in the presence of triflic acid. In the acid-catalyzed reactions, the reactivity of 1 in OAT of thioanisole was enhanced significantly, showing more than 10(4)-fold acceleration in rate. Electron transfer (ET) from electron donors to 1 also occurred only in the presence of HOTf. The enhanced reactivity of 1 by HOTf was explained by proton-coupled electron transfer from electron donors, such as ferrocene, to 1 in light of the Marcus theory of ET. The present study reports for the first time the dramatic proton effect on the chemical properties of metal-superoxo species.

引用

页码：8372 / 8375

页数：4

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