Journal of Organometallic Chemistry p. 158 - 167 (2002)
Update date:2022-08-05
Topics:
Maldanis, Richard J
Wood, John S
Chandrasekaran
Rausch, Marvin D
Chien, James C.W
Several Ni(II) α-diimine complexes have been synthesized and examined for ethylene and propylene polymerization in combination with different aluminum co-catalysts. The precatalysts used in the study were [ArN=C(Nap)-C(Nap)-C(Nap)=NAr]NiBr2 (Nap = 1,8-naphthdiyl) (1, Ar = 2,4,6-trimethylphenyl; 2, Ar = 2-tBu phenyl; 3, Ar = 2-iPr phenyl). These complexes were synthesized via a one-pot reaction where the ligand is formed via an acid catalyzed condensation followed by direct addition of nickel(II) bromide. The complexes were also prepared by a two-step procedure where the ligand was first formed by condensation between the appropriate aniline and acenapthoquinone, and the resulting ligand was then allowed to react with (1,2-dimethoxyethane) nickel(II) dibromide. X-ray structural studies of complexes 1 and 2 have been carried out. Diethylaluminum chloride (DEAC), and 1,3-dichloro-1,3-diisobutyldialuminoxane (DCDAO) show higher activities for ethylene and propylene polymerizations in combination with these Ni(II) α-diimine complexes than does polymethylaluminoxane (MAO). The molecular weight of the resulting polymers as well as their respective polydispersities and Tms are also presented. The polypropylenes obtained with 1/DEAC and 2/DEAC at 0 °C show similar rr triad percentage as previously reported for polypropylenes generated by MAO activated Ni(II) α-diimine complexes.
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