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
收藏
页码：8372 / 8375
页数：4
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