Introducing electron-donating substituents on ligand backbone of α-diimine nickel complex and the effects on catalyst thermal stability in ethylene polymerization.

Graphical abstract α-Diimine nickel catalyst Cat.1 with methyl-substituted naphthalene backbone was synthesized and investigated for ethylene polymerization. Compared with typical brookhart catalyst B-Cat , Cat.1 exhibited higher polymerization activity at elevated temperature. With union of experimental and computational methods, electronic effects was found to have significant effects on the thermal stability of α-diimine nickel catalysts. Highlights • Cat.1 with 2 -CH 3 S on naphthalene backbone was synthesized and investigated for ethylene polymerization. • Cat.1 exhibited better thermal stability as compared with typical Brookhart catalyst (B-Cat). • Cat.1 showed higher ratio of activated nickel and longer catalyst lifetime than B-Cat. • Methyl substituents made an electron-rich nickel center, enhancing thermal stability of Cat.1. Abstract A novel α-diimine nickel pre-catalyst Cat.1 with two electron-donating methyl substituents on the ligand backbone was synthesized and investigated for ethylene polymerization using methylaluminoxane as cocatalyst. Cat.1 exhibited higher polymerization activity and produced highly branched polyethylene with slightly higher molecular weight than that of the typical Brookhart catalyst (B-Cat) at elevated temperature. By tracing the changes of active center number in the polymerization process, Cat.1 was found to have higher ratio of activated nickel ([C∗]/[Ni]), longer catalyst lifetime and larger chain propagation rate constant (k p) as compared with B-Cat. The computational studies demonstrated the electron-donating methyl substituents can make a more electron-rich ligand to influence the catalytic properties of Cat.1. Stronger interactions between the electron-rich ligand and the nickel center should be the main reasons for longer catalyst lifetime and enhanced thermal stability of Cat.1. The production of polyethylene with higher molecular weight by Cat.1 can be explained by its larger k p value and more stable transition state for ethylene insertion than for chain transfer reaction due to the electron-donating ligand. Overall, the results of this work clearly support the importance of ligand electronic effects on the thermal stability and intrinsic reactivity of active centers in α-diimine Ni(II) catalysts. [ABSTRACT FROM AUTHOR]