Nickel Complexes of Allyl and Vinyldiphenylphosphine

Monophosphine-ligated nickel compounds e.g., [Ni(PPh3)4] are relevant as active catalysts across a broad range of reactions. This report expands upon the coordi-nation chemistry of this family, offering the reactivity of allyl- and vinyl-substituted diphenylphosphine (PPh2R) with [Ni(COD)2] (COD = 1,5-cyclooctadiene). These reac-tions provide three-coordinate dinickelacycles that are intermolecularly tethered through adjacent {Ni}-olefin interactions. The ring confirmation of such cycles has been studied in the solid-state and using theoretical calcula-tions. Here, a difference in reaction outcome is linked to the presence of an allyl vs. vinyl group, where the former is observed to undergo rearrangement, bringing about challenges in clean product isolation.