Investigations of the Ligand Electronic Effects on [1.0]-Diimine Nickel(II) Catalyzed Ethylene Polymerization

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 ˆ 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 ˆ 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.