Reversible O-O Bond Cleavage in Copper-Dioxygen Isomers: Impact of Anion Basicity
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- 作者：Xavier Ottenwaelder ; Deanne Jackson Rudd ; Mary C. Corbett ; Keith O. Hodgson ; Britt Hedman ; and T. Daniel P. Stack
- 刊名：Journal of the American Chemical Society
- 出版年：2006
- 出版时间：July 26, 2006
- 年：2006
- 卷：128
- 期：29
- 页码：9268 - 9269
- 全文大小：222K
- 年卷期：v.128,no.29(July 26, 2006)
- ISSN：1520-5126
文摘
Low-temperature oxygenation of copper(I) complexes of N,N,N',N'-tetraethylpropane-1,3-diamine yields solutions containing both 
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2:2-peroxodicopper(II) (P) and bis(-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.
-2:2-peroxodicopper(II) (P) and bis(-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.