Olefin Insertion into a Pd–F Bond: Catalyst Reactivation Following β‐F Elimination in Ethylene/Vinyl Fluoride Copolymerization

The discrete (phosphinoarenesulfonate)Pd fluoride complex (PO^Bp,OMe)PdF(lutidine), where PO^Bp,OMe=(2‐MeOC₆H₄)(2‐{2,6‐(MeO)₂C₆H₃}C₆H₄)(2‐SO₃‐5‐MeC₆H₃)P, inserts vinyl fluoride (VF) to form (PO^Bp,OMe)PdCH₂CHF₂(lutidine) and inserts multiple ethylene (E) units to generate polyethylene that contains ?CH₂F chain ends. These results provide strong evidence that the ?CHF₂ and ?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.