Reactions of substituted hydrazines with vanadium(III) compounds: Crystal structures of [NH(2)Me(2)](2)[(VCl3)(2)(mu-NNMe(2))(3)], [V(OC6H3Pr2i-2,6)(3)(NH(2)NMe(2))(2)] and [V(OC6H3Pr2i-2,6)(3)(NH(2)NMePh)2]

Reaction of Me(3)SiNHNMe(2) with [VCl3(PMePh(2))(2)] or [VCl3(thf)(3)] (thf = tetrahydrofuran) gave the triply hydrazide-bridged complex [NH(2)Me(2)](2)[(VCl3)(2)(mu-NNMe(2))(3)] 1 the crystal structure of which has been determined. Cyclic voltammetry shows 1 to have E(1/2)(ox) = 0.30 V (reversible at -35 degrees C) and E(2)(ox) = 1.35 V (vs. ferrocene-ferrocenium). Cation exchange gave [PPh(4)](2)[(VCl3)(2)(mu-NNMe(2))(3)] and reaction with Li(SC6H2Pr3i-2,4,6) gave [NH(2)Me(2)](2)[{V(SC6H2Pr3i-2,4,6)(3)}(2)(mu-NN(2)Me(2))(2)]. Treatment of [V(OC6H3Pr2i-2,6)(4)Li(thf)] with NH(2)NMe(2) gave the low-melting compound [V(OC6H3Pr2i-2,6)(3)(NH(2)NMe(2))(2)], shown by astructure determination to be essentially trigonal bipyramidal, with axial hydrazine ligands. The analogue [V(OC6H3Pr2i-2,6)(3)(NH(2)NMePh)(2)] has also been prepared and shown to have a similar structure.