An Anionic, Tetragonal Copper(II) Superoxide Complex

被引：97

作者：

Donoghue, Patrick J.

Gupta, Aalo K.

Boyce, David W.

Cramer, Christopher J.

Tolman, William B. ^{[1
]}

机构：

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

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2010年 / 132卷 / 45期

基金：

美国国家科学基金会;

关键词：

END-ON; BIS(MU-OXO) COMPLEXES; DIOXYGEN ACTIVATION; BINDING MODES; ACTIVE-SITE; REACTIVITY; LIGAND; ADDUCT; MONOOXYGENASE; HYDROXYLATION;

D O I：

10.1021/ja106244k

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Insight into copper-oxygen species proposed as intermediates in oxidation catalysis is provided by the identification of a Cu(II)-superoxide complex supported by a sterically hindered, pyridinedicarboxamide ligand. A tetragonal, end-on superoxide structure is proposed based on DFT calculations and UV-vis, NMR, EPR, and resonance Raman spectroscopy. The complex yields a trans-1,2-peroxodicopper(II) species upon reaction with [(tmpa)Cu(CH3CN)]OTf and, unlike other known Cu(II)-superoxide complexes, acts as a base rather than an electrophilic (H-atom abstracting) reagent in reactions with phenols.

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页码：15869 / 15871

页数：3

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