A dinickel catalyst promotes reductive cyclization reactions of 1,1-dichloroalkenes containing pendant olefins. The reactions can be conducted with a Zn reductant or electrocatalytically using a carbon working electrode. Mechanistic studies are consistent with the intermediacy of a Ni2(vinylidene) species, which adds to the alkene and generates a metallacyclic intermediate. β-Hydride elimination followed by C-H reductive elimination forms the cyclization product. The proposed dinickel metallacycle is structurally characterized and its stoichiometric conversion to product is demonstrated. Spin polarized, unrestricted DFT calculations are used to further examine the cyclization mechanism. These computational models reveal that both nickel centers function cooperatively to mediate the key oxidative addition, migratory insertion, β-hydride elimination, and reductive elimination steps.
Keywords: cyclization; electrocatalysis; metal–metal bonds; nickel; vinylidene.