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

Authors :
Ottenwaelder X
Rudd DJ
Corbett MC
Hodgson KO
Hedman B
Stack TD
Source :
Journal of the American Chemical Society [J Am Chem Soc] 2006 Jul 26; Vol. 128 (29), pp. 9268-9.
Publication Year :
2006

Abstract

Low-temperature oxygenation of copper(I) complexes of N,N,N',N'-tetraethylpropane-1,3-diamine yields solutions containing both mu-eta2:eta2-peroxodicopper(II) (P) and bis(mu-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.

Details

Language :
English
ISSN :
0002-7863
Volume :
128
Issue :
29
Database :
MEDLINE
Journal :
Journal of the American Chemical Society
Publication Type :
Academic Journal
Accession number :
16848427
Full Text :
https://doi.org/10.1021/ja061132g