Concerted steric and electronic effects on α-diimine nickel- and palladium-catalyzed ethylene polymerization and copolymerization.

For transition metal-based olefin polymerization catalysts, ligand steric and electronic effects can strongly influence important catalytic properties. However, the simultaneous tuning of both steric and electronic effects has not been explored in most of the previous studies. In this contribution, a strategy to tune the ligand electronic and steric effects in a concerted fashion is reported. In such a system, both dibenzhydryl groups and multiple methoxy/fluoro groups were installed in α-diimine ligands. In addition to strongly influencing ligand electronics, the methoxy/fluoro groups can interact with the dibenzhydryl groups and efficiently increase ligand sterics. In ethylene polymerization, this concurrent tuning of electronic and steric effects can lead to simultaneous enhancement of several parameters (activity, stability, polymer molecular weight, melting point, branching density) for both the nickel and palladium catalysts. The effectiveness of this strategy is highly attractive for future studies in other catalytic systems.