Selective Ethylene Dimerization into 2-Butenes Using Homogeneous and Supported Nickel(II) 2-Iminopyridine Catalysts

In this work, we report a series of novel nickel(II) dibromide and dichloride complexes with 2-iminopyridine and 2-iminoquinoline ligands bearing electron-withdrawing substituents (F, Cl, CF₃), that have demonstrated high ethylene dimerization activity [up to 19.2 × 10⁶ g of oligomers·(mol Ni)⁻¹ h⁻¹] in the presence of MAO or Et₂AlCl, affording predominantly a mixture of 1-butene and cis- and trans-2-butene (C₄ selectivity varies from 89 to 100%; 2-butenes selectivity in the C₄ fraction approaches 96%). The effects of ligand substituents and the cocatalyst nature on the activity and selectivity of the nickel(II) complexes in ethylene dimerization have been established. Several nickel complexes were supported on silica-alumina and the resulting heterogeneous catalysts were probed towards ethylene dimerization. These catalysts also afford 2-butenes, with the activity and C₄ selectivity being comparable to that of homogeneous catalysts.