Reactivity of dioxygen-copper systems

被引：1128

作者：

Lewis, EA

Tolman, WB

机构：

[1] Univ Minnesota, Dept Chem, Minneapolis, MN 55455 USA

[2] Univ Minnesota, Ctr Met Biocatalysis, Minneapolis, MN 55455 USA

来源：

CHEMICAL REVIEWS | 2004年 / 104卷 / 02期

关键词：

D O I：

10.1021/cr020633r

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The mechanism by which copper complexes bind and activate dioxygen was analyzed. The kinetic and thermodynamic information was obtained through cryogenic stopped-flow studies of the oxygenation of Cu(I) compounds. It was shown that protonation or acylation of peroxo copper species appears to enhance their O-atom transfer reactivity. It was concluded that O-O homolysis or heterolysis in CuOOH(R) complexes is energetically disfavored because of thermodynamic instability of the resulting Cu(III/IV)-oxo species.

引用

页码：1047 / 1076

页数：30

共 295 条

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