The crystalline trilithium salt Li3[N3N] (N3N = [(Me3SiNCH2CH2)3N]3-) reacts with VCl4(DME) (DME = 1,2-dimethoxyethane) to give [N3N]VCl in 45% yield. The structure of [N3N]VCl, as determined by X-ray crystallography, is a distorted trigonal bipyramid with three equatorial silylamido groups and axial chloride and amine donor ligands. Reduction of [N3N]VCl with Na/Hg in pentane provides trigonal monopyramidal V[N3N] in >90% yield. V[N3N] deoxygenates propylene oxide, cis-or trans-2-butene oxide, pyridine N-oxide, nitrous oxide, or dimethyl sulfoxide to produce [N3N]V=O. Treatment of V[N3N] with either S8 or ethylene sulfide gives [N3N]V=S, while gray selenium reacts with V[N3N] to give black crystalline [N3N]V=Se. PMe3 abstracts selenium from [N3N]V=Se, forming Me3P=Se and regenerating V[N3N]. Elemental tellurium does not react with V[N3N], but when V[N3N] is treated with Me3P=Te in toluene under vacuum, [N3N]V=Te can be observed by NMR in solution. The chalcogenide complexes [N3N]V=X(X = O,S,Se,Te) were characterized by V-51 NMR. Shifts ranged over 1600 ppm, with the more electronegative chalcogens producing greater upfield V-51 chemical shifts. V[N3N] reacts with trimethylsilyl azide to give [N3N] V=NSiMe3. [N3N]V=NSiMe3 also could be prepared by reducing [N3N]VN3 With Na/Hg, followed by treatment with Me3SiCl. V[N3N] reacts with C5H5NNC6F5 to give rust-red [N3N]V=NC6F5 and with (trimethylsilyl)diazomethane to give [N3N]V=N-N=CH(SiMe3). [N3N]V=N(p-CH3C6H4) was prepared by adding a solution of Li3[N3N] to C13V=N(p-CH3C6H4) in ether. An NH group transfers from 2-methylaziridine to V[N3N], liberating propylene and forming yellow, crystalline [N3N]V=NH. [N3N]V=NH may be deprotonated and then silylated to give [N3N]V=NSiMe3. The structure of [N3N]V=NH was determined by X-ray crystallography. The imido hydrogen was located and refined; the V=N-H unit is nearly linear (173(6)degrees), and the V-N(imido) bond length is 1.638(6) angstrom. The V-N(amine), bond length (2.241(6) angstrom) is comparable to that in [N3N]VCl (2.238(6) angstrom). The structure of [N3N]V=NH is compared and contrasted with the structures of [N3N]VCl and V[N3N’] (N3N’ = [It-BuMe2SiNCH2CH2)3N]3-).