Selective Chain-End Functionalization of Polar Polyethylenes: Orthogonal Reactivity of Carbene and Polar Vinyl Monomers in Their Copolymerization with Ethylene.

Pd(II)-catalyzed copolymerization of ethylene, carbene species, and polar vinyl monomers is successfully developed for the first time to obtain chain-end-functionalized polar polyethylenes, with selective distribution of the polar vinyl monomers within the main chain and carbene at the chain-end. Notably, >99% chain-end-capping with the carbene species can be achieved under the optimized conditions. Mechanistic investigations suggest that the carbene precursor reacts with the generated alkyl palladium complex to terminate the growing chain-end and regenerate the catalyst.