Methylene Bridged P(III) and P (V) Phosphiniminato-Phosphanes: Versatile Ligands And Substituents for Metals and Metalloids

Abstract

Abstract Recent studies1 have shown that the mono oxidized phosphanolminatophosphane Me3SiN=PPh2CH2PPh2 1 is a versatile ligand for a variety of transition metals in high and low oxidation states. This heterodifunctional ligand may bind to metals via the “hard” (N) or the “soft”(P(III)) centres; the former favours high oxidation states and “early” transition metals, the latter, low oxidation states and “late” transition metals. Monodentate or bidentate complexation is observed and in the latter case chelation or bridging is possible. Elimination of Me3SiCl from a metal halide or migration of Me3Si group to a terminal oxygen atom leads to metal nitrogen sigma bond formation. To modify the basicity at nitrogen a variety of approaches have been employed. Metathetical elimination of Me3SiX from activated halogenated aromatics leads to functionalisation at N. The R3Sn and R3Ge analogs of 1 have also been made by extensions of the Staudinger reaction. Reactions of 1 and its N-aromatic, N-Ge, and N-Sn analogs wi...