Phosphane, phosphite, phosphido complexes of vanadium(V)

Article abstract of DOI:10.1002/zaac.19976230807

Complex formation of tert-butylimidovanadium(V)trichloride (1) with phosphanes und phosphites has been studied. Syntheses of phosphidovanadium(V) compounds ^tC₄H₉N=VCp(NH^tC₄H ₉)[P(SiMe₃)₂] and ^tC₄H₉N=VCp(NⁱProp ₂)(PR₂) (R = SiMe₃, Ph) are described starting from the corresponding chlorovanadium(V) complexes. The reaction of 1 with silver hexafluorophosphate yields a bis(fluoro)phosphidovanadium(IV) complex [(μ-PF₂)₂V₂Cl₂(N ^tC₄H₉)₂]; as primary intermediate product of the unknown redox reaction a cationic vanadium(V) complex [^tC₄H₉N=VCl₂ · PPh₃]⁺PF₆^- has been isolated. 1 reacts with an excess of diisopropylamine forming ^tC₄H₉N=V(NⁱProp₂)Cl ₂ (16); in addition the following diisopropylamido-tert-butylimidovanadium(V) compounds ^tC₄H₉N=VCp(NⁱProp₂)Cl (3) and ^tC₄H₉N=V(NⁱProp₂)X ₂ (X = CH₂CMe₃, O^tC₄H₉, CH₃COO) has been prepared. All compounds obtained are characterized by ¹H, ⁵¹V, ³¹P NMR spectroscopy. The X-ray diffraction analysis of 16 and 3 indicate a planar coordination sphere of the amido nitrogen atom.