Synthesis and X‐ray Molecular Structure of (PNP) 2 [Mo IV (C 6 H 4 S 2 ‐1,2) 3 ] Completing the Structural Characterization of the Series [Mo(C 6 H 4 S 2 ‐1,2) 3 ] n – ( n = 0, 1, 2)

The tris(benzene‐1,2‐dithiolato) complex (Li) 2 [Mo IV (C 6 H 4 S 2 ‐1,2) 3 ] {(Li) 2 [Mo IV (bdt) 3 ]} (bdt 2– = C 6 H 4 S 2 ‐1,2 dianion) was synthesized from [MoCl 4 (CH 3 CN) 2 ], (H 2 bdt), and n BuLi in THF. Complex (Li) 2 [Mo IV (bdt) 3 ] undergoes aerial oxidation to give Li[Mo V (bdt) 3 ]. Both complexes were crystallized from methanol as the salts (PNP) 2 [Mo IV (bdt) 3 ] and (PNP)[Mo V (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= 24.8°) while the coordination geometry of [Mo V (bdt) 3 ] – is best described as distorted octahedral (average twist angle= 34.1°). (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)