The Reactions of Dioxobis(acetylacetonato)moIybdenum, MoO2(acac)2, with Tetrathiomolybdate and Tetrathiotungstate. High Formation Tendency of the {Mvi(μ-S)2Miv} (μ-S )2MVI} Group and the [MVI,S3(S2)]2- Type Ligand (M = Mo, W)

Abstract

1 Tetraphenylphosphonium tetrathiometalates, (PPh4)2MS4 (M = Mo, W), react with MoO2 (acac)2 (2:1) in boiling acetonitrile in redox processes to give mixed-crystal compounds (as expected) of the approximate composition (PPh4)2[Mo3O1.9S8.1] (1) and (PPh4)2[Mo1.4W1.6O1.3S8.3] (2), respectively. and 2 were characterized by single crystal X-ray structure analyses. The various anions o f 1 and 2 contain {MVI(μ-S)2MoIVO (μ-S )2MVI} cores (M = Mo (1); Mo, W (2); bond angle M ··· Mo ··· M = 151.3° (1) 152.2 - 154.3° (2)), which have high formation tendencies. The terminal positions are occupied by S and O atoms. The trinuclear anions of 1 correspond to the type [XYMo(μ-S)2MoO(μ-S)2MoSX ]2- (X = O, S; Y = S, S2). In 2 there are two sets of anions of the type [XYM(μ-S)2MoO(μ-S)2WS2]2- and [ZSM (μ-S)2MoO(μ-S)2MZS]2- (Z = Sn/Om) in the ratio o f 2:1, occupying two symmetry-independent sites in the unit cell. Complex 2 is the first structurally characterized mixed-metal Mo - W thiometalate.