Flexible Axial Shielding Strategy for Improving Ethylene (Co)polymerization with 8-Cycloalkylnaphthyl α-Diimine...

8-aryl or alkyl-naphthyl substituents are widely used as an effective axial shielding strategy for the suppression of chain transfer in late-transition metal-catalyzed ethylene (co)polymerization to yield high molecular weight polyethylene and copolymers. In this study, two 8-cycloalkylnaphthyl acenaphthene-based α-diimine ligands and the corresponding four nickel and palladium complexes were designed and synthesized to explore the effect of axial flexible shielding on ethylene (co)polymerization. In ethylene polymerization, the nickel complexes displayed high activities (up to 1.99 × 10⁶ g mol^-1 h^-1) and generated lightly branched (34-54/1000 C) polyethylenes with high molecular weights (up to M = 1075 kg/mol), whereas the corresponding palladium complexes exhibited moderate activities (level of 10⁴ g mol^-1 h^-1), producing highly branched (111-125/1000 C) polyethylenes with high molecular weights (up to M = 37.6 kg/mol). Highly branched (110-123/1000 C) E-MA copolymers with moderate insertion ratios (1.97-5.56 mol %) were produced by these palladium complexes in ethylene/methyl acrylate (MA) copolymerization. In addition, the size of the 8-cycloalkyl ring in these α-diimine catalysts strongly influences the ethylene (co)polymerization. Compared to cyclopentyl groups, cyclohexyl groups are more effective in suppressing chain transfer reactions in the polymerization of ethylene and the copolymerization of ethylene and MA, leading to higher molecular weight polyethylene and E-MA copolymers. Most interestingly, compared to the reported rigid planar 8-arylnaphthyl catalysts, the flexible 8-cyclohexylnaphthyl catalysts exhibited higher activity and produced higher molecular weight polyethylene in ethylene polymerization. Moreover, in nickel-catalyzed ethylene polymerization, the cyclohexyl catalyst produced significantly reduced branched polyethylene, while in palladium-catalyzed ethylene (co)polymerization, the cyclohexyl catalyst produced more highly branched polyethylene and copolymers. In contrast to the previously reported flexible 8-butylnaphthyl nickel catalysts, the 8-cycloalkylnaphthyl catalysts reported in this work yielded polyethylene with narrow unimodal molecular weight distributions.