title: Reversible cleavage and formation of the dioxygen O-O bond within a dicopper complex.
abstract: A key step in dioxygen evolution during photosynthesis is the oxidative generation of the O-O bond from water by a manganese cluster consisting of M2(mu-O)2 units (where M is manganese). The reverse reaction, reductive cleavage of the dioxygen O-O bond, is performed at a variety of dicopper and di-iron active sites in enzymes that catalyze important organic oxidations. Both processes can be envisioned to involve the interconversion of dimetal-dioxygen adducts, M2(O2), and isomers having M2(mu-O)2 cores. The viability of this notion has been demonstrated by the identification of an equilibrium between synthetic complexes having [Cu2(mu-eta2:eta2-O2)]2+ and [Cu2(mu-O)2]2+ cores through kinetic, spectroscopic, and crystallographic studies.
authors.affiliation: Department of Chemistry, University of Minnesota, Minneapolis, MN 55455, USA.
authors.forename: J A
authors.initials: JA
authors.lastname: Halfen
authors.forename: S
authors.initials: S
authors.lastname: Mahapatra
authors.forename: E C
authors.initials: EC
authors.lastname: Wilkinson
authors.forename: S
authors.initials: S
authors.lastname: Kaderli
authors.forename: V G
authors.initials: VG
authors.lastname: Young
authors.forename: L
authors.initials: L
authors.lastname: Que
authors.forename: A D
authors.initials: AD
authors.lastname: Zuberbühler
authors.forename: W B
authors.initials: WB
authors.lastname: Tolman
mesh_terms: D055598:Chemical Phenomena; D002627:Chemistry, Physical; D003300:Copper / Q000737:chemistry*; D018360:Crystallography, X-Ray; D006571:Heterocyclic Compounds / Q000737:chemistry; D009942:Organometallic Compounds / Q000737:chemistry; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry*; D013056:Spectrophotometry, Ultraviolet; D013059:Spectrum Analysis, Raman; D013696:Temperature
chemical_list: C098528:(1,4,7-tribenzyl-1,4,7-triazacyclononane-N,N',N'')(methylcyano)copper chlorate; C098529:(1,4,7-triisopropyl-1,4,7-triazacyclonanane-N,N',N'')(methylcyano)copper trifluoromethylsulfonate; D006571:Heterocyclic Compounds; D009942:Organometallic Compounds; D003300:Copper; D010100:Oxygen