title: A trinuclear intermediate in the copper-mediated reduction of O2: four electrons from three coppers.
abstract: The reaction of metal complexes with dioxygen (O2) generally proceeds in 1:1, 21, or 41 (metal:O2) stoichiometry. A discrete, structurally characterized 31 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.
authors.affiliation: Department of Chemistry, Stanford University, Stanford, CA 94305, USA.
authors.forename: A P
authors.initials: AP
authors.lastname: Cole
authors.forename: D E
authors.initials: DE
authors.lastname: Root
authors.forename: P
authors.initials: P
authors.lastname: Mukherjee
authors.forename: E I
authors.initials: EI
authors.lastname: Solomon
authors.forename: T D
authors.initials: TD
authors.lastname: Stack
mesh_terms: D003300:Copper / Q000737:chemistry / Q000378:metabolism*; D018360:Crystallography, X-Ray; D004583:Electrons; D009682:Magnetic Resonance Spectroscopy; D010084:Oxidation-Reduction; D010088:Oxidoreductases / Q000737:chemistry / Q000378:metabolism; D010100:Oxygen / Q000378:metabolism*; D013056:Spectrophotometry, Ultraviolet; D013696:Temperature
chemical_list: D003300:Copper; D010088:Oxidoreductases; D010100:Oxygen