title: Reversible O-O bond cleavage in copper-dioxygen isomers: impact of anion basicity.
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.
authors.affiliation: Department of Chemistry, Stanford University, Stanford, California 94305, USA.
authors.forename: Xavier
authors.initials: X
authors.lastname: Ottenwaelder
authors.forename: Deanne Jackson
authors.initials: DJ
authors.lastname: Rudd
authors.forename: Mary C
authors.initials: MC
authors.lastname: Corbett
authors.forename: Keith O
authors.initials: KO
authors.lastname: Hodgson
authors.forename: Britt
authors.initials: B
authors.lastname: Hedman
authors.forename: T Daniel P
authors.initials: TD
authors.lastname: Stack
mesh_terms: D000838:Anions / Q000737:chemistry; D003300:Copper / Q000737:chemistry*; D007536:Isomerism; D008958:Models, Molecular; D015394:Molecular Structure; D010100:Oxygen / Q000737:chemistry*
chemical_list: D000838:Anions; D003300:Copper; D010100:Oxygen