title: Electrophilic phosphonium cations (EPCs) with perchlorinated-aryl substituents: towards air-stable phosphorus-based Lewis acid catalysts.
abstract: A series of phosphines incorporating (C6Cl5) substituents, Ph2P(C6Cl5) 1, PhP(C6Cl5)22, P(C6Cl5)33 and (C6F5)P(C6Cl5)24 were prepared. In the case of 1, 2 and 4, these were converted to the corresponding aryl-difluorophosphoranes 5-7via reaction with XeF2, whereas reaction of 3 with XeF2 afforded only an inseparable mixture of products. The compounds 5-7 were converted to the fluorophosphonium cations 8-10, whereas the reaction of 3 with Selectfluor afforded (C6Cl5)2POF and (C6Cl5)2. The fluorophosphonium salts showed evidence of improved air stability as well as Lewis acid catalytic activity in hydrodefluorination, hydrosilylation, deoxygenation and dehydrocoupling chemistry.
authors.affiliation: Department of Chemistry, University of Toronto, 80 St. George St., Toronto, Ontario M5S 3H6, Canada. dstephan@chem.utoronto.ca.
authors.forename: Shawn
authors.initials: S
authors.lastname: Postle
authors.forename: Vitali
authors.initials: V
authors.lastname: Podgorny
authors.forename: Douglas W
authors.initials: DW
authors.lastname: Stephan