Dicopper and heteronuclear iron-copper peroxo complex formation: kinetics and thermodynamics.
Quasireversible adducts of dioxygen with Cu(I) complexes are of interest as models for dioxygen transport proteins, for oxygen-dependent copper redox enzymes, and for low-molecular oxidation and oxygenation catalysts. Depending on ligand denticity and structural factors dioxygen binds in various geometries and metal:O2 ratios to the reduced copper centers. Kinetic investigations produce detailed mechanistic insight into the nature of coppers-dioxygen interaction. Heteronuclear FeO2Cu complexes with stabilities far beyond statistical expectation are obtained when 1:1 mixtures of suitable copper(I) complexes and appropriate Fe(II) porphyrins are treated with O2.
Zuberbühler
Andreas D
AD
Department of Chemistry, Spitalstrasse 51, University of Basel, CH-4056 Basel, Switzerland. andreas.zuberbuehler@unibas.ch