Nickel Complexes of Allyl and Vinyldiphenylphosphine

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