Biomimetic Binding and Activation of Dioxygen with Copper Complexes

Abstract

Synthetically derived copper(I) coordination complexes have been used to study O 2 -binding and copper mediated oxidation/oxygenations, of interest and relevance in chemical and biological processes. Three spectroscopically and structurally distinct types of {LCu 2 -O 2 } complexes are described, where each Cu(I) n (n = 1,2) precursor is able to bind O 2 reversibly. Reactivity comparisons show that two of the three species possess nucleophilic or basic peroxo ligands, while the other has a non-basic O 2 2- ligand also acting as an electrophile. The latter complex is suggested to have a μ-η 2 :η 2 peroxo coordination. This type of species is also present in a reaction system mimicking copper monooxygenases; here, the {Cu 2 -O 2 } intermediate is able to hydroxylate an arene substrate which is part of the dinucleating ligand.