title: Olefin Insertion into a Pd-F Bond: Catalyst Reactivation Following β-F Elimination in Ethylene/Vinyl Fluoride Copolymerization.
abstract: The discrete (phosphinoarenesulfonate)Pd fluoride complex (POBp,OMe)PdF(lutidine), where POBp,OMe=(2-MeOC6H4)(2-{2,6-(MeO)2C6H3}C6H4)(2-SO3-5-MeC6H3)P, inserts vinyl fluoride (VF) to form (POBp,OMe)PdCH2CHF2(lutidine) and inserts multiple ethylene (E) units to generate polyethylene that contains -CH2F chain ends. These results provide strong evidence that the -CHF2and -CH2F chain ends in E/VF copolymer generated by (phosphinoarenesulfonate)PdR catalysts form by β-F elimination of Pd(β-F-alkyl) species, VF or E insertion of the resulting (PO)PdF species, and subsequent chain growth. These results also imply that β-F elimination is not an important catalyst deactivation reaction in this system.
authors.affiliation: Department of Chemistry, The University of Chicago, 5735 South Ellis Avenue, Chicago, IL, 60637, USA.|Permanent address: New Product R&D Center, Technology General Division, Asahi Glass Co., LTD., 1150 Hazawa-cho, Kanagawa-ku, yokohama-shi, Kanagawa, 221-8755, Japan.
authors.forename: Shinji
authors.identifier: 0000-0002-5132-123X
authors.initials: S
authors.lastname: Wada
authors.affiliation: Department of Chemistry, The University of Chicago, 5735 South Ellis Avenue, Chicago, IL, 60637, USA.
authors.forename: Richard F
authors.identifier: 0000-0002-3158-4745
authors.initials: RF
authors.lastname: Jordan
keywords: copolymerization; fluorides; olefin insertion; phosphine-sulfonate complex; β-F elimination