A series of 2-(1-arylimino)ethyl-9-arylimino-5,6,7,8-tetrahydrocycloheptapyridine derivatives was synthesized and fully characterized, and thereafter reacted with iron dichloride to form their corresponding iron(II) complexes. The single crystals of representative organic and iron complex compounds were obtained and analyzed by the X-ray diffraction analysis, indicating the distorted bipyramidal geometry around the iron core. Moreover, DFT calculations were performed on selected species to determine their structural features. On treatment with either MAO or MMAO, all iron complex pre-catalysts showed high activities (up to 1.56 × 10⁷ gPE mol⁻¹(Fe) h⁻¹) toward ethylene polymerization. Regarding the nature of the ligands and reaction parameters, their catalytic activities and the characters of the obtained polyethylenes have been carefully investigated. The ring strain of the fused-cycloheptane of the ligands within iron complexes was considered to affect their catalytic performance in ethylene polymerization. The active species were activated and controlled by using a co-catalyst of MMAO preferred over MAO, and the obtained polyethylenes with MMAO showed narrower molecular polydispersity than the corresponding polyethylenes with MAO.

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.

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 10⁴ 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 series of 1-[2-(bis(4-fluorophenyl)methyl)-4,6-dimethylphenylimino]-2-aryliminoacenaphthylene derivatives together with the corresponding nickel bromide complexes was synthesized and characterized. Representative complexes C2 and C5 were characterized by the single-crystal X-ray diffraction, revealing a distorted tetrahedral geometry. Upon activation with either methylaluminoxane (MAO) or ethylaluminum sesquichloride (EASC), all nickel complexes exhibited high activities towards ethylene polymerization, producing polyethylene with a relatively low degree of branching and narrow polydispersity. Complex C1 maintained good activity at elevated reaction temperatures, which indicates significant thermal stability of the active species.