Phosphorus-Atom Transfer from Phosphaethynolate to an Alkylidyne

A low-spin and mononuclear vanadium complex, ((Me)nacnac)V(CO)(eta(2)-P equivalent to(CBu)-Bu-t) (2) ((Me)nacnac(-)=[ArNC(CH3)](2)CH, Ar=2,6-(Pr2C6H3)-Pr-i), was prepared upon treatment of the vanadium neopentylidyne complex ((Me)nacnac)V equivalent to(CBu)-Bu-t(OTf) (1) with Na(OCP)(diox)(2.5) (diox=1,4-dioxane), while the isoelectronic ate-complex [Na(15-crown-5)]{([ArNC(CH2)]CH[C(CH3)NAr])V(CO)(eta(2)-P equivalent to(CBu)-Bu-t)} (4), was obtained via the reaction of Na(OCP)(diox)(2.5) and ([ArNC(CH2)]CH[C(CH3)NAr])V equivalent to(CBu)-Bu-t(OEt2) (3) in the presence of crown-ether. Computational studies suggest that the P-atom transfer proceeds by [2+2]-cycloaddition of the P equivalent to C bond across the V equivalent to(CBu)-Bu-t moiety, followed by a reductive decarbonylation to form the V-C equivalent to O linkage. The nature of the electronic ground state in diamagnetic complexes, 2 and 4, was further investigated both theoretically and experimentally, using a combination of density functional theory (DFT) calculations, UV/Vis and NMR spectroscopies, cyclic voltammetry, X-ray absorption spectroscopy (XAS) measurements, and comparison of salient bond metrics derived from X-ray single-crystal structural characterization. In combination, these data are consistent with a low-valent vanadium ion in complexes 2 and 4. This study represents the first example of a metathesis reaction between the P-atom of [PCO](-) and an alkylidyne ligand.