{Bis[N,N′-(2-alkyl-6-para-methylphenyl)phenyl)imino]acenaphthene}dibromonickel catalysts bearing bulky methylphenyl groups: synthesis, characterization, crystal structures and application in catalytic polymerization of ethylene and styrene

Abstract

Two new Ni(II) complexes containing methylphenyl groups, {bis[N,N′-(2,6-dimethyl-4-p-methylphenylphenyl)imino]acenaphthene}dibromonickel 4a and {bis[N,N′-(2-ethyl-4,6-di(p-methylphenyl)phenyl)imino]acenaphthene}dibromonickel 4b, were synthesized and characterized. The molecular structures of both complexes were determined by single-crystal X-ray diffraction. Both complexes have pseudo-tetrahedral geometry about the nickel center, showing pseudo C 2v and C 2 molecular symmetry, respectively. Complex 4c, {bis[N,N′-(2,4,6-trimethylphenyl)imino]acenaphthene}dibromonickel, was also synthesized for comparison. These complexes were tested as catalysts for the polymerization of ethylene and styrene under mild conditions using diethylaluminum chloride. The precatalyst 4b bearing one ortho-ethyl group and two bulky p-methylphenyl groups in the ortho- and para-aryl position of the ligand, displayed highly catalytic activity for the polymerization of ethylene [4.70 × 106 g PE/(mol Ni h bar)], and produced branched polyethylene (76 methyl, 8 ethyl, 5 propyl and 22 butyl or longer branches/1,000 C at 60 °C). Interestingly, complex 4b also displays high catalytic activity [5.46 × 105 g polystyrene/(mol Ni·h)] for styrene polymerization and produces nearly atactic polystyrene at 70 °C (stereo-triad distributions: rr, 39.9 %; mr, 30.4 %; mm, 29.8 %; stereo-diad distributions: r, 55.1 %; m, 44.9 %).