title: Dicopper peroxo complexes: low temperature stopped-flow reaction kinetics of [(BQPA)CuI]+ and [(Me2-TMPA)CuI]+.
abstract: In the last 20 years, the reaction of many different CuI complexes and with dioxygen has been described. There is quite a big variety in their coordination geometry and most of them have been characterized by X-ray crystallography. Beyond structural information, stopped-flow kinetics experiments have provided additional mechanistic insights. In the particular systems [(BQPA)CuI]+ and [(Me2-TMPA)CuI]+ a new equilibrium between the two species trans-mu-1,2-peroxo and bis-mu-oxo is demonstrated. In the case of [(BQPA)CuI]+ the two species are in an equilibrium, presumably via the transient superoxo species. The reaction of [(Me2-TMPA)CuI]+ with dioxygen leads to the parallel formation of both species. The kinetically preferred trans-mu-peroxo species is then isomerised to the thermodynamically more stable bis-mu-oxo species.
authors.affiliation: Department of Chemistry, University of Basel, Spitalstrasse 51, 4056 Basel, Switzerland. patrick.wick@unibas.ch
authors.forename: P K
authors.initials: PK
authors.lastname: Wick
authors.forename: K D
authors.initials: KD
authors.lastname: Karlin
authors.forename: M
authors.initials: M
authors.lastname: Suzuki
authors.forename: Andreas D
authors.initials: AD
authors.lastname: Zuberbühler