Reversible O-O bond cleavage in copper-dioxygen isomers: Impact of anion basicity

被引：55
作者：
Ottenwaelder, Xavier
Rudd, Deanne Jackson
Corbett, Mary C.
Hodgson, Keith O. [1 ]
Hedman, Britt
Stack, T. Daniel P.
机构：
[1] Stanford Univ, Dept Chem, Stanford, CA 94305 USA
[2] Stanford Linear Accelerator Ctr, Stanford Synchrotron Radiat Lab, Stanford, CA 94309 USA
来源：
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2006年 / 128卷 / 29期
关键词：
D O I：
10.1021/ja061132g
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
Low-temperature oxygenation of copper(I) complexes of N,N,N′,N′-tetraethylpropane-1,3-diamine yields solutions containing both μ-η2:η2-peroxodicopper(II) (P) and bis(μ-oxo)dicopper(III) (O) valence isomers. The P/O equilibrium position depends on the nature of the counteranion; P is favored with more basic anions. Titration and EXAFS experiments as well as DFT calculations suggest that axial donation from a sulfonate anion to the copper centers imparts an electronic/electrostatic bias toward the P isomer. Copyright © 2006 American Chemical Society.
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页码：9268 / 9269
页数：2
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