Aromatic hydroxylation of anthracene derivatives by a chromium(iii)-superoxo complex via proton-coupled electron transfer

被引:3
|
作者
Devi, Tarali [1 ]
Lee, Yong-Min [1 ]
Nam, Wonwoo [1 ]
Fukuzumi, Shunichi [1 ,2 ]
机构
[1] Ewha Womans Univ, Dept Chem & Nano Sci, Seoul 03760, South Korea
[2] Meijo Univ, Fac Sci & Engn, Nagoya, Aichi 4688502, Japan
基金
日本科学技术振兴机构;
关键词
MONONUCLEAR NONHEME IRON; OXYGEN-ATOM TRANSFER; C-H ACTIVATION; MULTIELECTRON OXIDATION; IRON(IV)-OXO COMPLEX; DIOXYGEN ACTIVATION; METAL-OXO; REACTIVITY; COPPER; MODEL;
D O I
10.1039/c9cc03245b
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The chemistry of metal-superoxo intermediates started being unveiled in oxidation reactions by enzymes and their synthetic model compounds. However, aromatic hydroxylation reactions by the metal-superoxo species are yet to be demonstrated. In this study, we report for the first time that the hydroxylation of aromatic compounds such as anthracene and its derivatives by a mononuclear nonheme Cr(iii)-superoxo complex, [(Cl)(TMC)Cr-III(O-2)](+) (1), occurs in the presence of triflic acid (HOTf) via the rate-determining proton-coupled electron transfer (PCET) from anthracene to 1, followed by a fast further oxidation to give anthraquinone. The rate constants of electron transfer from anthracene derivatives to 1 in the presence of HOTf are well analyzed in light of the Marcus theory of electron transfer.
引用
收藏
页码:8286 / 8289
页数:4
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