Zygmunt Flisak

Constrained formation of 2-(1-(arylimino)ethyl)-7-arylimino-6,6-dimethylcyclopentapyridines and their cobalt(II) chloride complexes: synthesis, characterization and ethylene polymerization

A series of 2-(1-(arylimino)ethyl)-7-arylimino-6,6-dimethylcyclopentapyridine derivatives (L1-L5) was synthesized, and individually reacted with cobalt(II) chloride to form the corresponding cobalt chloride complexes (C1-C4). These compounds were characterized, and the single crystal X-ray diffraction for two representative cobalt complexes was carried out. The molecular structures indicate that 2,7-bis(arylimino)cyclopentapyridines act as tridentate ligands; however, one of the Co-N coordinative bonds is weak due to the spatial separation of nitrogen atoms. Upon activation with either MAO or MMAO, all cobalt complexes exhibit catalytic activities toward ethylene. Polymerization takes place in the presence of MAO with activities of approximately 10(4) g of PE per (mol of Co) per h, but oligomerization occurs in the presence of MMAO with the activities higher by one order of magnitude. The resultant products, either polyethylenes or oligomers, display high linearity. Relatively low activities observed for cobalt complexes discussed reflect the importance of the appropriate spatial arrangement of the three donor nitrogen atoms.

A practical ethylene polymerization for vinyl-polyethylenes: synthesis, characterization and catalytic behavior of α,α′-bisimino-2,3:5,6-bis(pentamethylene)pyridyliron chlorides

A series of α,α′-bis(arylimino)-2,3:5,6-bis(pentamethylene)pyridyliron chlorides was synthesized in a one-pot reaction and characterized by FT-IR and elemental analysis as well as X-ray crystallography for one representative iron complex, where the Fe center adopts a distorted square pyramidal geometry with three coordinating nitrogen and two chlorine atoms. The iron precatalysts, upon treatment with either methylaluminoxane (MAO) or modified methylaluminoxane (MMAO), exhibit high activities in the range of 107 g of PE per mol of Fe per h toward ethylene polymerization, yielding highly linear and, more importantly, vinyl-polyethylenes. The correlation between the structural features of iron complexes and their catalytic activities was also investigated.