Synthesis and X-ray molecular structure of (PNP)2[MOIV(C6H4S2-1,2)3] completing the structural characterization of the series [Mo(C6H4S2-1,2)3]n- (n=0, 1, 2)

The tris (benzene-1,2-dithiolato) complex (Li)(2)[MOIV(C(6)H(4)S(2)1,2)(3)] [Mo-IV(bdt)(3)]} (bdt(2-) = C6H4S2-1,2 dianion) was synthesized from [MOCl4(CH3CN)(2)], (H(2)bdt), and nBuLi in THF. Complex (Li)(2)[Mo-IV(bdt)(3)] undergoes aerial oxidation to give Li[Mov(bdt)3]. Both complexes were crystallized from methanol as the salts (PNP)(2)[Mo-IV(bdt)(3)] and (PNP)[MoV- (bdt)(3)] {PNP+ = bis (triphenylphosphoranylidene) ammonium cation), and their molecular structures were determined by X-ray diffraction. The molybdenum(IV) complex [Mo-IV-(bdt)(3)](2-) assumes a distorted trigonal prismatic coordination geometry (average twist angle rho = 24.8 degrees) while the coordination geometry of [Mo-V(bdt)(3)](-) is best described as distorted octahedral (average twist angle rho = 34.1 degrees).