Synthesis of Vanadium(III), -(IV), and -(V) Complexes That Contain the Pentafluorophenyl-Substituted Triamidoamine Ligand [(C6F5NCH2CH2)3N]3-

[N 3 N]V O ([N 3 N] 3 - = [(C 6 F 5 NCH 2 CH 2 ) 3 N] 3 - ) was prepared from VOCl 3 and H 3 [N 3 N] in the presence of Et 3 N. Related arylimido complexes, [N 3 N]V NAr (Ar = p -MeC 6 H 4, p -CF 3 C 6 H 4, or p -FC 6 H 4 ), were prepared in high yields from the known V(NAr)Cl 3 (THF) complexes in a similar manner or by treating [N 3 N]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 VCl 3 (THF) 3 and H 3 [N 3 N] in the presence of triethylamine gave [HNEt 3 ]{[N 3 N]VCl} ( 3 ) when the reaction was carried out in ether and [N 3 N]V(CH 3 CN) ( 4a ) when carried out in acetonitrile, while the reaction between VCl 3 (THF) 3 and H 3 [N 3 N] in the presence of triethylamine and tert -butyl isocyanide gave green [N 3 N]V( t -BuNC). [N 3 N]V(CH 3 CN) reacts with propylene oxide to give [N 3 N]V O and with diazoalkanes to give [N 3 N]V NN CHR (R = SiMe 3, CO 2 C 2 H 5 ). An X-ray structure determination of 4a (C 26 H 15 N 5 F 15 V, a = 13.021(1) Å, b = 13.021(1) Å, c = 14.221(1) Å, γ = 120°, rhombohedral, R 3 (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 [N 3 N]V(THF) ( 5 ). An X-ray structure determination of 5 (C 28 H 20 N 4 F 15 OV, a = 15.390(7) Å, b = 12.189(6) Å, c = 16.468(7) Å, β = 109.96 (3)°, monoclinic, P 2 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 ]{[N 3 N]VCl} reacts with ferrocenium triflate to yield [N 3 N]VCl, a species that can be reduced to 5 in THF by sodium amalgam.