Reactivity of dioxygen-copper systems

被引：1140
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.
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页码：1047 / 1076
页数：30
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