Living Polymerization of Ethylene and Copolymerization of Ethylene/Methyl Acrylate Using “Sandwich” Diimine Palladium Catalysts

Cationic Pd­(II) catalysts incorporating bulky 8-<i>p</i>-tolylnaphthyl substituted diimine ligands have been synthesized and investigated for ethylene polymerization and ethylene/methyl acrylate copolymerization. Homopolymerization of ethylene at room temperature resulted in branched polyethylene with narrow <i>M</i>_w/<i>M</i>_n values (ca. 1.1), indicative of a living polymerization. A mechanistic study revealed that the catalyst resting state was an alkyl olefin complex and that the turnover-limiting step was migratory insertion, thus the turnover frequency is independent of ethylene concentration. Copolymerization of ethylene and methyl acrylate (MA) was also achieved. MA incorporation was found to increase linearly with MA concentration, and copolymers with up to 14 mol % MA were prepared. Mechanistic studies revealed that acrylate insertion into a Pd–CH₃ bond occurs at −70 °C to yield a four-membered chelate, which isomerizes first to a five-membered chelate and then to a six-membered chelate. Barriers to migratory insertion of both the (diimine)­PdCH₃(C₂H₄)⁺ (19.2 kcal/mol) and (diimine)­PdCH₃(η²-C₂H₃CO₂Me)⁺ (15.2 kcal/mol) were measured by low-temperature NMR kinetics