title: Olefin isomerization and hydrosilylation catalysis by Lewis acidic organofluorophosphonium salts.
abstract: Organofluorophosphonium salts of the formula [(C6F5)(3-x)Ph(x)PF][B(C6F5)4] (x = 0, 1) exhibit Lewis acidity derived from a low-lying σ* orbital at P opposite F. This acidity is evidenced by the reactions of these salts with olefins, which catalyze the rapid isomerization of 1-hexene to 2-hexene, the cationic polymerization of isobutylene, and the Friedel-Crafts-type dimerization of 1,1-diphenylethylene. In the presence of hydrosilanes, olefins and alkynes undergo efficient hydrosilylation catalysis to the alkylsilanes. Experimental and computational considerations of the mechanism are consistent with the sequential activation and 1,2-addition of hydrosilane across the unsaturated C-C bonds.
authors.affiliation: Department of Chemistry, University of Toronto , 80 St. George Street, Toronto, Ontario M5S 3H6, Canada.
authors.forename: Manuel
authors.initials: M
authors.lastname: Pérez
authors.forename: Lindsay J
authors.initials: LJ
authors.lastname: Hounjet
authors.forename: Christopher B
authors.initials: CB
authors.lastname: Caputo
authors.forename: Roman
authors.initials: R
authors.lastname: Dobrovetsky
authors.forename: Douglas W
authors.initials: DW
authors.lastname: Stephan