title: "Oxidatively induced" reductive elimination of dioxygen from an eta2-peroxopalladium(II) complex promoted by electron-deficient alkenes.
abstract: The first example of associative displacement of dioxygen from a peroxopalladium(II) complex is reported. Electron-deficient alkenes, p-X-trans-beta-nitrostyrene (X = OCH3, CH3, H, F, Br, CF3, NO2), react quantitatively with (bc)Pd(eta2-O2) (bc = bathocuproine) in dichloromethane at room temperature to form the corresponding palladium(0)-alkene complexes. Mechanistic studies indicate that ligand substitution proceeds through an associative mechanism, and the electronic characteristics of the reactions are consistent with an "oxidatively induced" reductive elimination pathway.
authors.affiliation: Department of Chemistry, University of Wisconsin-Madison, 1101 University Avenue, Madison, WI 53706, USA.
authors.forename: Brian V
authors.initials: BV
authors.lastname: Popp
authors.forename: Shannon S
authors.initials: SS
authors.lastname: Stahl
mesh_terms: D000475:Alkenes / Q000737:chemistry*; D016227:Benzoquinones / Q000737:chemistry; D002384:Catalysis; D009942:Organometallic Compounds / Q000737:chemistry; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry*; D010165:Palladium / Q000737:chemistry*; D010545:Peroxides / Q000737:chemistry
chemical_list: D000475:Alkenes; D016227:Benzoquinones; D009942:Organometallic Compounds; D010545:Peroxides; C004532:quinone; D010165:Palladium; D010100:Oxygen