Work

Reversible O−O Bond Cleavage in Copper−Dioxygen Isomers: Impact of Anion Basicity

Year: 2006

Type: article

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.

Source: Journal of the American Chemical Society

DOI: 10.1021/ja061132g

Authors: Xavier Ottenwaelder, Deanne Jackson Rudd, Mary C. Corbett, Keith O. Hodgson, Britt Hedman, T. Daniel P. Stack

Institutions: Stanford Synchrotron Radiation Lightsource, Stanford University

Language: English

Topic: Metal-Catalyzed Oxygenation Mechanisms

Subfield: Inorganic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: green

Funders: National Institute of General Medical Sciences, National Center for Research Resources

Awards: G113944070, G3379451020, DIOXYGEN ACTIVATION BY MODEL COPPER COMPLEXES, G4599067938, G6820916050