The discrete (phosphinoarenesulfonate)Pd fluoride complex (PO )PdF(lutidine), where PO =(2-MeOC H )(2-{2,6-(MeO) C H }C H )(2-SO -5-MeC H )P, inserts vinyl fluoride (VF) to form (PO )PdCH CHF (lutidine) and inserts multiple ethylene (E) units to generate polyethylene that contains -CH F chain ends. These results provide strong evidence that the -CHF and -CH F 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.
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