"Oxidatively induced" reductive elimination of dioxygen from an eta2-peroxopalladium(II) complex promoted by electron-deficient alkenes.
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.
Popp
Brian V
BV
Department of Chemistry, University of Wisconsin-Madison, 1101 University Avenue, Madison, WI 53706, USA.
Stahl
Shannon S
SS
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
D000475:Alkenes; D016227:Benzoquinones; D009942:Organometallic Compounds; D010545:Peroxides; C004532:quinone; D010165:Palladium; D010100:Oxygen