Living Polymerization of Ethylene and Copolymerization
of Ethylene/Methyl Acrylate Using “Sandwich” Diimine
Palladium Catalysts
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Abstract
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><sub>w</sub>/<i>M</i><sub>n</sub> 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–CH<sub>3</sub> 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)PdCH<sub>3</sub>(C<sub>2</sub>H<sub>4</sub>)<sup>+</sup> (19.2 kcal/mol) and (diimine)PdCH<sub>3</sub>(η<sup>2</sup>-C<sub>2</sub>H<sub>3</sub>CO<sub>2</sub>Me)<sup>+</sup> (15.2 kcal/mol) were measured by low-temperature NMR kinetics