[N3N]V=O ([N3N](3-) = [(C6F5NCH2CH2)(3)N](3-)) was prepared from VOCl3 and H-3[N3N] in the presence of Et(3)N. Related arylimido complexes, [N3N]V=NAr (Ar = p-MeC(6)H(4), p-CF3C6H4, or p-FC6H4), were prepared in high yields from the known V(NAr)Cl-3(THF) complexes in a similar manner or by treating [N3N]V=O with an aryl isocyanate in refluxing m-xylene. New imido complexes also were prepared by reacting an imido complex with an aryl isocyanate over a period of 2 days in refluxing mesitylene. The reaction between VCl3(THF)(3) and H-3[N3N] in the presence of triethylamine gave [HNEt(3)]{[N3N]VCl} (3) when the reaction was carried out in ether and [N3N]V(CH3CN) (4a) when carried out in acetonitrile, while the reaction between VCl3(THF)(3) and H-3[N3N] in the presence of triethylamine and tert-butyl isocyanide gave green [N3N]V(t-BuNC). [N3N]V(CH3CN) reacts with propylene oxide to give [N3N]V=O and with diazoalkanes to give [N3N]V=NN=CHR (R = SiMe(3), CO2C2H5). An X-ray structure determination of 4a (C26H15N5F15V, a = 13.021(1) Angstrom, b = 13.021(1) Angstrom, c = 14.221(1) Angstrom, gamma = 120 degrees, rhombohedral, R3 (h), Z = 3) shows it to be a pseudo-trigonal-bipyramidal species with acetonitrile coordinated in the apical position. An attempt to prepare the iodo analog of 3 by adding Me(3)SiI in THF to it yielded green crystalline [N3N]V(THF) (5). An X-ray structure determination of 5 (C28H20N4F15OV, a = 15.390(7) Angstrom, b = 12.189(6) Angstrom, c = 16.368(7) Angstrom, beta = 109.96 (3)degrees, monoclinic, P2(1)/n, Z = 4) shows it to be a pseudo trigonal bipyramid containing 1 equiv of THF in the axial position in a structure that otherwise is similar to that of 4a. [HNEt(3)]{[N3N]VCl} reacts with ferrocenium triflate to yield [N3N]VCl, a species that can be reduced to 5 in THF by sodium amalgam.