Sterically bulky diarylmethyl-based ligands have received increasing attention in the field of late-transition-metal catalyzed olefin polymerization. Ortho-substituents may have a significant impact on the performance of diarylmethyl-based α-diimine Pd catalysts. In this contribution, a series of α-diimine Pd catalysts bearing ortho-methoxyl/hydroxyl functionalized dibenzhydryl units were prepared, characterized, and investigated in ethylene polymerization and copolymerization with methyl acrylate (MA). The catalytic performances were improved by introducing more ortho-substituents. The catalysts exhibited good thermal stabilities at high temperatures, producing branched polyethylenes. The catalysts bearing hydroxyl groups possessing intramolecular H-bonding, resulted in slightly higher incorporation ratios of MA unit when compared with the catalysts bearing methoxyl groups.

The synthesis and characterization of a series of dibenzhydryl-based α-diimine Ni(II) complexes bearing a range of electron-donating or -withdrawing groups are described. Polymerization with ethylene is investigated in detail, involving the activator effect, influence of polymerization conditions on catalyst activity, thermal stability, polymer molecular weight and melting point. All of these Ni(II) complexes show great activity (up to 6 × 10⁶ g of PE (mol of Ni)-1·h-1), exceptional thermal stability (stable at up to 100 °C) and generate polyethylene with very high molecular weight (Mn up to 1.6 × 10⁶) and very narrow molecular weight distribution. In the dibromo Ni(II) system, the electronic perturbations exhibit little variation on the ethylene polymerization. In the Ni(acac) system, dramatic ligand electronic effects are observed in terms of catalytic activity and polyethylene molecular weight.

In this work, we studied propylene polymerization using some α-diimine palladium catalysts with systematically varied ligand sterics. In propylene polymerization, the ligand steric effect exhibits significant variations on the catalytic activity, polymer molecular weight, and branching density. However, the regio control for the polymer microstructure is poor. Furthermore, copolymerization of 1-octene with the highly challenging and biorenewable comonomer acrylic acid was investigated. High copolymer molecular weights and high comonomer incorporation ratios could be achieved in this system. This study provides a novel access for the direct synthesis of branched carboxylic acid functionalized polyolefins.