Lewis acidity of organofluorophosphonium salts: hydrodefluorination by a saturated acceptor.
Prototypical Lewis acids, such as boranes, derive their reactivity from electronic unsaturation. Here, we report the Lewis acidity and catalytic application of electronically saturated phosphorus-centered electrophilic acceptors. Organofluorophosphonium salts of the formula [(C6F5)(3-x)Ph(x)PF][B(C6F5)4] (x = 0 or 1; Ph, phenyl) are shown to form adducts with neutral Lewis bases and to react rapidly with fluoroalkanes to produce difluorophosphoranes. In the presence of hydrosilane, the cation [(C6F5)3PF](+) is shown to catalyze the hydrodefluorination of fluoroalkanes, affording alkanes and fluorosilane. The mechanism demonstrates the impressive fluoride ion affinity of this highly electron-deficient phosphonium center.
Department of Chemistry, University of Toronto, 80 St. George Street, Toronto, Ontario M5S 3H6, Canada.
Christopher B
CB
Caputo
Lindsay J
LJ
Hounjet
Roman
R
Dobrovetsky
Douglas W
DW
Stephan