Impact of o-aryl halogen effects on ethylene polymerization: steric vs. electronic effects†

Ligand steric hindrance and electronic effects play a crucial role in late-transition metal-catalyzed olefin polymerization. In this research, a series of o-aryl halogenated α-diimine ligands bearing bulky dibenzhydryl substituents, along with their corresponding nickel catalysts, have been synthesized and thoroughly characterized. The nickel catalysts demonstrated very high activity in ethylene polymerization, achieving a high rate of up to 10⁷ g mol⁻¹ h⁻¹. The produced polyethylenes displayed a broad spectrum of molecular weights (12.2–871.7 kg mol⁻¹) but maintained consistent branching densities (50–82/1000 C) when polymerized at a fixed temperature with different nickel catalysts. Notably, the polymerization temperature has a significant influence on both the molecular weight and branching density of the resulting polyethylene. Higher temperatures led to the formation of polyethylenes with lower molecular weights and increased branching densities. Interestingly, the o-aryl halogens significantly impact the molecular weight of the polyethylene. The size of the halogen substituents primarily determines the molecular weight of the polyethylene. However, in terms of branching density, the steric and electronic effects of these substituents appear to counteract each other. In addition, the branched high molecular weight polyethylenes from the bromine and chlorine substituted nickel catalysts are excellent polyethylene thermoplastic elastomers with high strain at break values (688–2478%) and high strain recovery values (42–62%).