Highly Linear Polyethylenes Achieved Using Thermo-Stable and Efficient Cobalt Precatalysts Bearing Carbocyclic-Fused NNN-Pincer Ligand.

Six examples of 2-(1-arylimino)ethyl-9-arylimino-5,6,7,8-tetrahydrocycloheptapyridine-cobalt(II) chloride complexes, [2-(1-ArN)C₂H₃-9-ArN-5,6,7,8-C₅H₈C₅H₃N]CoCl₂, (Ar = 2-(C₅H₉)-6-MeC₆H₃ Co1, 2-(C₆H11)-6-MeC₆H₃ Co2, 2-(C₈H15)-6-MeC₆H₃ Co3, 2-(C₅H₉)-4,6-Me₂C₆H₂ Co4, 2-(C₆H11)-4,6-Me₂C₆H₂ Co5, and 2-(C₈H15)-4,6-Me₂C₆H₂ Co6), were synthesized by the direct reaction of the corresponding ortho-cycloalkyl substituted carbocyclic-fused bis(arylimino)pyridines (L1⁻L6) and cobalt(II) chloride in ethanol with good yields. All the synthesized ligands (L1⁻L6) and their corresponding cobalt complexes (Co1⁻Co6) were fully characterized by FT-IR, ¹H/13C-NMR spectroscopy and elemental analysis. The crystal structure of Co2 and Co3 revealed that the ring puckering of both the ortho-cyclohexyl/cyclooctyl substituents and the one pyridine-fused seven-membered ring; a square-based pyramidal geometry is conferred around the metal center. On treatment with either methylaluminoxane (MAO) or modified methylaluminoxane (MMAO), all the six complexes showed high activities (up to 4.09 × 10⁶ g of PE mol-1 (Co) h-1) toward ethylene polymerization at temperatures between 20 °C and 70 °C with the catalytic activities correlating with the type of ortho-cycloalkyl substituent: Cyclopentyl (Co1 and Co4) > cyclohexyl (Co2 and Co5) > cyclooctyl (Co3 and Co6) for either R = H or Me and afforded strictly linear polyethylene (Tm > 130 °C). The narrow unimodal distributions of the resulting polymers are consistent with single-site active species for the precatalyst. Furthermore, compared to the previously reported cobalt analogues, the titled precatalysts exhibited good thermo-stability (up to 70 °C) and possessed longer lifetime along with a higher molecular weight of PE (Mw: 9.2~25.3 kg mol-1).