Organoimido and organodi-imido vanadium complexes

Autor: Ji-Fang Wu, Dale E. Wheeler, Eric A. Maatta
Rok vydání: 1998
Předmět:
Zdroj: Polyhedron. 17:969-976
ISSN: 0277-5387
DOI: 10.1016/s0277-5387(97)00222-2
Popis: 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 (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WCl4(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NC6H4NV(S2CNEt2)3], 11, and [( t BuO ) 3 V  NC 6 H 4 N  V(O t Bu ) 3 ] ,, 12, respectively.
Databáze: OpenAIRE
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