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.
引用
收藏
页码：15869 / 15871
页数：3
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