The vanadium(III) bis(neopentyl) complex (PNP)V(CH2tBu)2 (PNP = N[4-Me-2-(PiPr2)C6H3]2−), a complex readily prepared from alkylation of (PNP)VCl2 with 2 equiv of LiCH2tBu, serves as a precursor to the transient vanadium(III) alkylidene complex “(PNP)V═CHtBu”. Two-electron oxidation of the intermediate [(PNP)V═CHtBu] with chalcogen sources results in formation of the vanadium(V) chalcogenide series (PNP)V═CHtBu(X) (X = O, S, Se, Te). This family of chalcogenide−alkylidenes has been studied via 51V NMR spectroscopy in combination with DFT computational methods. The redox chemistry of [(PNP)V═CHtBu] and the reactivity of the alkylidene ligand are explored with the substrates N3SiMe3, N≡CtBu, N2, and azobenzene. It was discovered that N═N cleavage of the last substrate can be achieved without oxidation of the metal.