208239-73-0Relevant academic research and scientific papers
Organoimido and organodi-imido vanadium complexes
Wheeler, Dale E.,Wu, Ji-Fang,Maatta, Eric A.
, p. 969 - 976 (1998)
Reactions of the p-tolylimido vanadium(V) complex [V(NTol)Cl3], 1, with sodium dithiocarbamate salts Na[S2CNR2] yield an homologous series of organoimido vanadium(V) dithiocarbamate systems [TolN≡V(S2CNR2)xCl(3-x)] [x = 1 : R = Et (2a), Me (2b) ; x = 2 : R = Et (3a), Me (3b) ; x = 3 : R = Et (4a), Me (4b)]; the electronic and 51V NMR spectra of these complexes are described. Zn reduction of complexes 3 affords impure products whose ESR spectra are consistent with the presence of the V(IV) systems [V(NTol) (S2CNR2)2], 5. Reaction of VOCl3 with 0.5 equiv. of p-OCN - C6H4 - NCO yields the p-phenylenediimido complex [Cl3V≡NC6H4N=VCl3], 6. Dissolution of 6 in THF produces an adduct [(THF)3Cl3V≡ NC6H4N≡VCl3(THF)3], 7, whose THF ligands are weakly bound. VOCl3 reacts with an equimolar amount of p-OCN - C6H4 - NCO to produce the mononuclear complex p-[Cl3V≡NC6H4 - NCO], 8. The reaction of 8 with OWCl4 in refluxing toluene affords an insoluble product analyzing as the expected heterobinuclear system [Cl3V≡NC6H4N≡WCl4], 9, but treatment of this product with THF yields a mixture shown by 1H NMR to contain both 7 and its ditungsten analogue [(THF)Cl4W≡NC6H4N≡WCl 4(THF)], indicating that an unusual intermetallic exchange of imido ligands has occurred. The chloride ligands of 6 can be substituted by [S2CNEt2] or [OtBu] anions to afford [(Et2NCS2)3V≡NC6H 4N≡V(S2CNEt2)3], 11, and [(tBuO)3V≡NC6H 4N≡V(OtBu)3], 12, respectively.
