PHOSPHANE, PHOSPHITE, PHOSPHIDO COMPLEXES OF VANADIUM(V)

Complex formation of tert-butylimidovanadium(V)trichloride (1) with ph osphanes and phosphites has been studied. Syntheses of phosphidovanadi um(V) compounds (C4H9N)-C-t=VCp((NHC4H9)-C-t)[P(SiMe3)(2)] and (C4H9N) -C-t=VCp(N(i)Prop(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 [(mu-PF2)(2)V2Cl2((NC4H9)-C-t)(2)]; as primary intermediate pr oduct of the unknown redox reaction a cationic vanadium(V) complex [(C 4H9N)-C-t=VCl2 . PPh3]+PF6- has been isolated. 1 reacts with an excess of diisopropylamine forming (C4H9N)-C-t=V(N(i)Prop(2))Cl-2 (16); in a ddition the following diisopropylamido-tert-butylimidovanadium (V) com pounds (C4H9N)-C-t=VCp(N(i)Prop(2))Cl (3) and (C4H9N)-C-t=V(N(i)Prop(2 ))X-2 (X = CH2CMe3, (OC4H9)-C-t, CH3COO) has been prepared. All compou nds obtained are characterized by H-1, V-51, P-31 NMR spectroscopy. Th e X-ray diffraction analysis of 16 and 3 indicate a planar coordinatio n sphere of the amido nitrogen atom.