title: Spectroscopic and electronic structure studies of phenolate Cu(II) complexes: phenolate ring orientation and activation related to cofactor biogenesis.
abstract: A combination of spectroscopies and DFT calculations have been used to define the electronic structures of two crystallographically defined Cu(II)-phenolate complexes. These complexes differ in the orientation of the phenolate ring which results in different bonding interactions of the phenolate donor orbitals with the Cu(II), which are reflected in the very different spectroscopic properties of the two complexes. These differences in electronic structures lead to significant differences in DFT calculated reactivities with oxygen. These calculations suggest that oxygen activation via a Cu(I) phenoxyl ligand-to-metal charge transfer complex is highly endergonic (>50 kcal/mol), hence an unlikely pathway. Rather, the two-electron oxidation of the phenolate forming a bridging Cu(II) peroxoquinone complex is more favorable (11.3 kcal/mol). The role of the oxidized metal in mediating this two-electron oxidation of the coordinated phenolate and its relevance to the biogenesis of the covalently bound topa quinone in amine oxidase are discussed.
authors.affiliation: Department of Chemistry, Stanford University, Stanford, California 94305, USA.
authors.forename: Somdatta
authors.initials: S
authors.lastname: Ghosh
authors.forename: Jordi
authors.initials: J
authors.lastname: Cirera
authors.forename: Michael A
authors.initials: MA
authors.lastname: Vance
authors.forename: Tetsuya
authors.initials: T
authors.lastname: Ono
authors.forename: Kiyoshi
authors.initials: K
authors.lastname: Fujisawa
authors.forename: Edward I
authors.initials: EI
authors.lastname: Solomon
mesh_terms: D003300:Copper / Q000737:chemistry*; D018360:Crystallography, X-Ray; D004578:Electron Spin Resonance Spectroscopy; D004583:Electrons; D062385:Hydroxybenzoates / Q000737:chemistry*; D008958:Models, Molecular; D008968:Molecular Conformation; D010100:Oxygen / Q000737:chemistry; D013059:Spectrum Analysis, Raman; D013997:Time Factors
chemical_list: D062385:Hydroxybenzoates; D003300:Copper; C017616:phenolic acid; D010100:Oxygen