title: Experimental and computational study of a direct O2-coupled Wacker oxidation: water dependence in the absence of Cu salts.
abstract: The kinetics of the Pd[(-)-sparteine]Cl(2) catalyzed oxidation of decene using oxygen as the sole oxidant have been studied in the absence of copper salts and high [Cl(-)]. Saturation kinetics are observed for [decene] as well as a third order dependence on [water]. A mechanism is proposed involving the dissociation of two chlorides and rate-limiting formation of a three-water hydrogen bridged network and subsequent oxypalladation as supported by computational studies.
authors.affiliation: Department of Chemistry, University of Utah, 315 S 1400 E, Salt Lake City, Utah 84112-085, USA.
authors.forename: Brian J
authors.initials: BJ
authors.lastname: Anderson
authors.forename: John A
authors.initials: JA
authors.lastname: Keith
authors.forename: Matthew S
authors.initials: MS
authors.lastname: Sigman
mesh_terms: D000447:Aldehydes / Q000138:chemical synthesis* / Q000737:chemistry; D000475:Alkenes / Q000737:chemistry*; D002384:Catalysis; D003198:Computer Simulation; D018360:Crystallography, X-Ray; D007700:Kinetics; D008958:Models, Molecular; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry*; D010165:Palladium / Q000737:chemistry; D013034:Sparteine / Q000737:chemistry; D014867:Water / Q000737:chemistry*
chemical_list: D000447:Aldehydes; D000475:Alkenes; D009942:Organometallic Compounds; D014867:Water; D013034:Sparteine; D010165:Palladium; D010100:Oxygen