Vinyl-addition polymerization of norbornene catalyzed by (pyrazol-1-ylmethyl)pyridine divalent iron, cobalt and nickel complexes

Complexes of 2-((3,5-dimethyl)-1H-pyrazol-1-ylmethyl)pyridine (L1), 2-((3,5-ditert-butyl-1H-pyrazol-1-yl)methyl)pyridine (L2), 2-((3,5-diphenyl)-1H-pyrazol-1-yl)methyl)pyridine (L3), 2-((3,5-bis(trifluoromethyl)-1H-pyrazol-1-ylmethyl)pyridine (L4) and 2,6-bis(3,5-dimethyl-1H-pyrazol-1-yl)methyl)pyridine (L5) with cobalt(II), iron(II) and nickel(II), Ni(L1)Cl2 (1), Co(L1)Cl2 (2), Fe(L1)Cl2 (3), Ni(L2)Cl2 (4), Ni(L3)Cl2 (5), Co(L3)Cl2 (6), Fe(L3)Cl2 (7), Ni(L4)Cl2 (8) and Ni(L5)Cl2 (9), were used as catalyst precursors to produce vinyl-addition type norbornene polymers. Both the identity of the metal center and nature of ligand affected the polymerization behaviour of the resultant catalysts. Nickel catalysts were generally more active than the corresponding iron and cobalt analogues. The polynorbornene produced have high molecular weights (0.5–2.1 × 106 g/mol) and narrow molecular weight distributions. Analyses of polymer microstructure using NMR and IR spectroscopy confirmed the polymers produced to be vinyl-addition polynorbornene.

Activation of 2-(pyrazolylmethyl)pyridine and 2,6-bis(pyrazolylmethyl)pyridine nickel complexes with MAO produce active catalysts for the vinyl-addition polymerization of norbornene to give high molecular weight polymers. Analogous iron and cobalt complexes show lower catalytic activities under similar conditions.Figure optionsDownload as PowerPoint slideHighlights
► (Pyrazolyl)pyridine nickel catalysts precursors.
► Precursors produce highly active vinyl-addition norbornene polymerization catalysts.
► Polymers have high and narrow molecular weights.