New neutral nickel(II) complexes bearing pyrrole-imine chelate ligands: synthesis, structure and norbornene polymerization behavior

Abstract

New neutral nickel(II) complexes bearing nonsymmetric bidentate pyrrole-imine chelate ligands ( 4a– d), [2-(ArNCH)C 4H 3N]Ni(PPh 3)Ph [Ar2,6-diisopropylphenyl ( a), 2-methyl-6-isopropylphenyl ( b), 2,6-diethylphenyl ( c), 2- tert-butylphenyl ( d)], have been prepared in good yields from the sodium salts of the corresponding ligands and trans-Ni(PPh 3) 2(Ph)Cl, and the structure of complex 4a has been confirmed by X-ray crystallographic analysis. These neutral Ni(II) complexes were investigated as catalysts for the vinylic polymerization of norbornene. Using modified methylaluminoxane (MMAO) as a cocatalyst, these complexes display very high activities and produce great mass polymers. Catalyst activity of up to 4.2×10 7 g (mol Ni h) −1 and the viscosity-average molecular weight of polymer of up to 9.2×10 5 g mol −1 were observed. Catalyst activity, polymer yield, and polymer molecular weight can be controlled over a wide range by the variation of reaction parameters such as Al–Ni ratio, norbornene–catalyst ratio, monomer concentration, polymerization reaction temperature and time.