A comprehensive picture on catalyst structure construction in palladium catalyzed ethylene (co)polymerizations

Abstract Late transition metal palladium catalysts chelated by benchmark α-diimine, phosphine-sulfonate, bisphosphine-monoxide ligands are of great interest for ethylene polymerization and challenging copolymerization with polar comonomers. Compared to numerous studies on the classic α-diimine and phosphine-sulfonate palladium catalysts, the new generation bisphosphine-monoxide palladium (BPMO-Pd) system is far less investigated. In this contribution, by skillfully designing a family of BPMO-Pd catalysts bearing differed steric and electronic P(III) phosphine groups, differed steric and electronic O = P(V) phosphine monoxide groups, and different connectivity of them, a comprehensive picture on catalyst structure construction is built for ethylene (co)polymerizations. This constructed catalyst structure-polymerization property relationship paves the way for the development of more efficient late transition metal catalysts for olefin (co)polymerization.