| Herein, a well-defined, neutral, phosphine-sulfonate ligated, palladium catalyst for the production of polyethene, poly(ethene-co-carbon monoxide, and polyethene-block-poly-(ethene-alt-carbon monoxide) co-oligomers is reported. The system is living under mild conditions and produces poly(ethene-co-carbon monoxide) with carbon monoxide content ranging from 0--50mol%. Mechanistic studies suggest that an unusually small difference in the ethene and carbon monoxide binding affinities as well as enhanced decarbonylation play important roles in determining the copolymer composition. Furthermore, this system was found to be exceptionally tolerant of polar functional-groups, protic solvents, and aqueous emulsion. This allows for the production of copolymers of ethene with polar monomers, including functionalized norbornenes and styrenes. Finally, the effects of anions and N-substituted imines on the palladium-catalyzed copolymerization of imines with carbon monoxide was investigated. |
