Vanadium alkylidynes: Rarely reported species with remarkable reactivity

The reactivity of early transition metal alkylidynes is quite ill-explored given the challenges in their syntheses. Recently, we aimed to investigate the reactivity of the only examples of vanadium alkylidyne complexes supported by β-diketiminate, (BDI)V≡C^tBu(OTf), and deprotonated β-diketiminate, (dBDI)V≡C^tBu(OEt₂) (dBDI²⁻= ArNC(CH₃)CHC(CH₂)NAr, Ar = 2,6-ⁱPr₂C₆H₃) in reaction with unsaturated molecules, ranging from P-atom transfer from sodium phosphaethynolate and unique reactivity with sodium arsaethynolate, to the cycloaddition reactions of the V≡C bond with hetereoalkynes and cyclic polymerization reaction with terminal alkynes. This system has provided us the opportunity to probe the mechanism of these reactions, both theoretically and experimentally, to better understand the remarkable reactivity and potential applications of early transition metal alkylidynes, the results of which will be presented here.