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)

Abstract

AbstractThe tris(benzene‐1,2‐dithiolato) complex (Li)2[MoIV(C6H4S2‐1,2)3] {(Li)2[MoIV(bdt)3]} (bdt2– = C6H4S2‐1,2 dianion) was synthesized from [MoCl4(CH3CN)2], (H2bdt), and nBuLi in THF. Complex (Li)2[MoIV(bdt)3] undergoes aerial oxidation to give Li[MoV(bdt)3]. Both complexes were crystallized from methanol as the salts (PNP)2[MoIV(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 [MoIV(bdt)3]2– assumes a distorted trigonal prismatic coordination geometry (average twist angle= 24.8°) while the coordination geometry of [MoV(bdt)3]– is best described as distorted octahedral (average twist angle= 34.1°). (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)