177778-11-9Relevant articles and documents
Synthesis of Vanadium (III), -(IV), and -(V) Complexes That Contain the Pentafluorophenyl-Substituted Triamicloamine Ligand [(C6F5NCH2CH2)3N] 3-
Nomura, Kotohiro,Schrock, Richard R.,Davis
, p. 3695 - 3701 (2008/10/09)
[N3N]V=O ([N3N]3- = [(C6F5NCH2CH2)3N] 3-) was prepared from VOCl3 and H3[N3N] in the presence of Et3N. Related arylimido complexes, [N3N]V=NAr (Ar = p-MeC6H4, p-CF3C4H4, or p-FC6H4), were prepared in high yields from the known V(NAr)Cl3(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 H3[N3N] in the presence of triethylamine gave [HNEt3]{[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 H3[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 = SiMe3, CO2C2H5). An X-ray structure determination of 4a (C26H15N5F15V, a = 13.021(1) ?, b = 13.021(1) ?, c = 14.221(1) ?, γ = 120°, 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 Me3SiI in THF to it yielded green crystalline [N3N]V(THF) (S). An X-ray structure determination of 5 (C28H20N4F15OV, a = 15.390(7) ?, b = 12.189(6) ?, c = 16.468(7) ?, β= 109.96 (3)°, monoclinic, P21/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. [HNEt3]{[N3N]VCl} reacts with ferrocenium triflate to yield [N3N]VCl, a species that can be reduced to 5 in THF by sodium amalgam.