A 1:1 copper-dioxygen adduct is an end-on bound superoxo copper(II) complex which undergoes oxygenation reactions with phenols

被引：157

作者：

Maiti, Debabrata

Fry, H. Christopher

Woertink, Julia S.

Vance, Michael A.

Solomon, Edward I.

Karlin, Kenneth D. ^{[1
]}

机构：

[1] Johns Hopkins Univ, Dept Chem, Baltimore, MD 21218 USA

[2] Stanford Univ, Dept Chem, Stanford, CA 94305 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2007年 / 129卷 / 02期

关键词：

D O I：

10.1021/ja067411l

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Employing a strongly electron-donating tripodal tetradentate ligand along with a reaction strategy designed to suppress binuclear peroxo complex formation, an end-on bound superoxo-copper(II) complex [Cu-II(NMe2-TMPA)(O-2(-))](+) (1) has been generated in solution [UV-vis (THF, -85 degrees C): lambda(max) = 418 nm (epsilon, 4300 M-1 cm-1), 615 nm (epsilon, 1100), 767 nm (epsilon, 840)]. Resonance Raman spectroscopy employing isotopically substituted dioxygen (including mixed isotope O-16/18(2)) proves the end-on superoxo Cu-II(O-2(-)) structural formulation, nu(O-O) = 1121 cm(-1); nu(Cu-O) = 472 cm(-1). The first demonstration of Cu-II(O-2(-)) oxidative reactivity with exogenous substrates, likely involving H-atom abstraction chemistry, comes with the finding that 1 effects the oxygenation and hydroperoxylation of substituted phenols.

引用

页码：264 / 265

页数：2

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