Abstract: | VCl3(NPPh3)(OPPh3)], a Phosphorane Iminato Complex of Vanadium(IV) The title compound has been prepared from vanadium tetrachloride and Me3SiNPPh3 in the presence of OPPh3 in CCl4 solution, forming orange-red, moisture sensitive crystals, which were characterized by an X-ray structure determination. Space group Cc, Z = 4, 2 560 observed unique reflections, R = 0.049. Lattice dimensions at 0°C: a = 1 018(1), b = 1 826(2), c = 1 859(2) pm, β = 93.65(9)° VCl3(NPPh3)(OPPh3)] forms monomeric molecules, in which the vanadium atom is coordinated in a distorted square pyramidal fashion with the (NPPh3)? ligand in apical position. The three chlorine atoms and the oxygen atom of the OPPh3 molecule occupy the basal positions. The phosphorane iminato group V?N?PPh3 is nearly linear (bond angle VNP 161.4°), the bond lengths VN (169 pm) and PN (162 pm) correspond with double bonds. |