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