Nickel Complexes of Allyl and Vinyldiphenylphosphine
Marissa L Clapson1, David J Nelson2, Marcus W Drover1
1Department of Chemistry and Biochemistry, The University of Windsor, 401 Sunset Avenue, Windsor, ON N9B 3P4, Canada.
Abstract:
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 of this family, offering the reactivity of allyl- and vinyl-substituted diphenylphosphine (PPh2R) with [Ni(COD)2] (COD = 1,5-cyclooctadiene). These reactions provide three-coordinate dinickelacycles that are intermolecularly tethered through adjacent {Ni}-olefin interactions. The ring conformation of such cycles has been studied in the solid-state and using theoretical calculations. 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.
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