Retro-Brook rearrangement induces the formation of an octahedral nickel(benzamidinate) complex; synthesis, structure and catalytic activity

The neutral octahedral nickel complex (PhC(NSiMe₃)NC(Ph)CHSiMe₃)Ni(acac)(TMEDA) (7), has been synthesized and characterized including X-ray diffraction analysis. The complex was formed by the reaction of Ni(acac)₂(TMEDA) with the lithium salt of the corresponding β-diketiminate ligand. The formation of the benzamidinate motif from the corresponding β-diketiminate is a consequence of a retro-Brook isomerization that is operative only at the nickel centre. A plausible mechanism for the metal mediated isomerization is proposed. When complex 7 was activated with MAO it showed a good catalytic activity for the addition polymerization of norbornene. Furthermore, this catalytic system has been found to oligomerize ethylene to a mixture of butenes and hexenes with a high turnover frequency, η = 29,300 h⁻¹, when the reaction is performed in dichloromethane.