Origin of Suppressed Chain Transfer in Phosphinephenolato Ni(II)-Catalyzed Ethylene Polymerization

Recent breakthroughs in the generation of polar-functionalized and more sustainable degradable polyethylenes have been enabled by advanced phosphinephenolato Ni-(II) catalysts. A key has been to overcome this type of catalysts' propensity for extensive chain transfer to enable formation of high-molecular-weight polyethylene chains. We elucidate the mechanistic origin of this paradigm shift by a combined experimental and theoretical study. Single-crystal X-ray structural analysis and cyclic voltammetry of a set of six different catalysts with variable electronics and sterics, combined with extensive pressure reactor polymerization studies, suggest that an attractive Ni-aryl interaction of a P-[2-(aryl)-phenyl] is responsible for the suppression of chain transfer. This differs from the established picture of steric shielding found for other prominent late transition metal catalysts. Extensive density functional theory studies identify the relevant pathways of chain growth and chain transfer and show how this attractive interaction suppresses chain transfer.