A Trinuclear Intermediate in the Copper-Mediated Reduction of O2: Four Electrons from Three Coppers

Science  27 Sep 1996:
Vol. 273, Issue 5283, pp. 1848-1850
DOI: 10.1126/science.273.5283.1848


The reaction of metal complexes with dioxygen (O2) generally proceeds in 1:1, 2:1, or 4:1 (metal:O2) stoichiometry. A discrete, structurally characterized 3:1 product is presented. This mixed-valence trinuclear copper cluster, which contains copper in the highly oxidized trivalent oxidation state, exhibits O2 bond scission and intriguing structural, spectroscopic, and redox properties. The relevance of this synthetic complex to the reduction of O2 at the trinuclear active sites of multicopper oxidases is discussed.