The Reactions of Dioxobis ( acetylacetonato ) moIybdenum , M o 0 2 ( acac

T etraphenylphosphonium tetrathiom etalates, (PPh4)^MS4 (M = M o, W), react with M oO ,(acac)2 (2:1) in boiling acetonitrile in redox processes to give mixed-crystal com pounds (as expected) o f the approxim ate com position (P P h ^ M o ^ O , 9Sg,] (1) and (PPh4)2[Moj 4W, 60 , 3Sg 3] (2), respectively. 1 and 2 were characterized by single crystal X-ray structure analyses. The various anions o f 1 and 2 contain {M VI(/i-S)2M oIV0 (//-S )2M VI} cores (M = M o (1); M o, W (2); bond angle M M o M = 151.3° (1) 152.2154.3° (2)), which have high form ation tendencies. The term inal positions are occupied by S and O atom s. The trinuclear anions o f 1 correspond to the type [X YM o(/i-S)2M oO (//-S)2M oSX]2' (X = O, S; Y = S, S2). In 2 there are two sets o f anions o f the type [XYM(/y-S)2M oO(//-S)2W S2]2“ and [ZSM (/i-S)2M oO(Jw-S)2M ZS]2̂ (Z = Sn/O m) in the ratio o f 2:1, occupying two sym metry-independent sites in the unit cell. Complex 2 is the first structurally characterized mixed-metal M o W thiom etalate.