Reversible O−O Bond Cleavage in Copper−Dioxygen Isomers: Impact of Anion Basicity
- 1 July 2006
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 128 (29) , 9268-9269
Abstract
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.Keywords
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