The complex [VCl3(PPh2Me)2] has been prepared from [VCl3(MeCN)3] or [VCl3(thf)3] (thf = tetrahydrofuran) and the tertiary phosphine in toluene. In the crystal there are two independent trigonal-bipyramidal molecules with axial phosphine ligands. There is considerable distortion from regular co-ordination polyhedra and mean bond distances are V-Cl, 2.22 and 2.23 Å and V-P, 2.54 and 2.53 Å. On long reflux of a solution of [VCl3(MeCN)3] and PPh2Me in toluene, the complex [VCl3(MeCN)(PPh2Me)2] is obtained. It contains six-co-ordinate vanadium(III) with meridional V-Cl bonds of average length 2.30 Å. Other bond distances are V-N, 2.140(3) Å and V-P, 2.56 Å (av.).
