title: Studies of reductive elimination reactions to form carbon-oxygen bonds from Pt(IV) complexes.
abstract: The platinum(IV) complexes fac-L(2)PtMe(3)(OR) (L(2) = bis(diphenylphosphino)ethane, o-bis(diphenylphosphino)benzene, R = carboxyl, aryl; L = PMe(3), R = aryl) undergo reductive elimination reactions to form carbon-oxygen bonds and/or carbon-carbon bonds. The carbon-oxygen reductive elimination reaction produces either methyl esters or methyl aryl ethers (anisoles) and L(2)PtMe(2), while the carbon-carbon reductive elimination reaction affords ethane and L(2)PtMe(OR). Choice of reaction conditions allows the selection of either type of coupling over the other. A detailed mechanistic study of the reductive elimination reactions supports dissociation of the OR(-) ligand as the initial step for the C-O bond formation reaction. This is followed by a nucleophilic attack of OR(-) upon a methyl group bound to the Pt(IV) cation to produce the products MeOR and L(2)PtMe(2). C-C reductive elimination proceeds from L(2)PtMe(3)(OR) by initial L (L = PMe(3)) or OR(-) (L(2) = dppe, dppbz) dissociation, followed by C-C coupling from the resulting five-coordinate intermediate. Our studies demonstrate that both C-C and C-O reductive elimination reactions from Pt(IV) are more facile in polar solvents, in the presence of Lewis acids, and for OR(-) groups that contain electron withdrawing substituents.
authors.affiliation: Department of Chemistry, University of Washington, P.O. Box 351700, Seattle, WA 98195-1700, USA.
authors.forename: B S
authors.initials: BS
authors.lastname: Williams
authors.forename: K I
authors.initials: KI
authors.lastname: Goldberg
mesh_terms: D006358:Hot Temperature; D007700:Kinetics; D010084:Oxidation-Reduction; D010984:Platinum / Q000737:chemistry*
chemical_list: D010984:Platinum