Solvent and co-catalyst dependent pyrazolylpyridinamine and pyrazolylpyrroleamine nickel(II) catalyzed oligomerization and polymerization of ethylene

Abstract

The pyrazolylamine ligands, 2-(3,5-dimethyl-1H-pyrazol-1-yl)-N-(pyridin-2-ylmethyl)ethan-amine (L1a), 2-(3,5-di-tert-butyl-1H-pyrazol-1-yl)-N-(pyridin-2-ylmethyl)ethan-amine (L2a), 2-(3,5-dimethyl-pyrazol-1-yl)-ethyl-(1H-pyrrol-2-ylmethyl)-amine (L3a), 2-(3,5-di-tert-butyl-pyrazol-1-yl)-ethyl-(1H-pyrrol-2-ylmethyl)-amine (L4a), were prepared by reducing the corresponding imine compounds L1–L4. L1a–L4a were then reacted with [NiBr2(DME)] to form the nickel complexes, [NiBr2(L1a)] (1), [NiBr2(L2a)] (2), [NiBr2(L3a)] (3) and [NiBr2(L4a)] (4) in high yields.When activated with aluminum co-catalysts, all four nickel complexes were able to catalyze the oligomerization or polymerization of ethylene; but the products of these reactions were co-catalyst and solvent dependent. With EtAlCl2 as co-catalyst and in toluene, butene and hexene were formed, which subsequently alkylated the solvent selectively to butyl-, dibutyl- and tri-butyltoluene. The same catalysts in chlorobenzene produced butene, hexene and highly branched polyethylene. Changing the co-catalysts to MAO and with toluene as solvent, complexes 2 and 3 catalyzed the polymerization of ethylene to high molecular weight (447,300Da) linear high density polyethylene (ca Tm=135.5°C); with polydispersity indices ranging from 1.63 to 2.51.