Reactions of Triangular Molybdenum and Tungsten Clusters with Tetrabromocatechol

The reaction of cluster complex (nBu4N)2[Mo3Se7Br6] with tetrabromocatechol (H2Tbc) in the presence of Et3N and Ph4PBr results in the formation of (Ph4P)2[Mo3Se7(Tbc)3]∙2MeOH (Ia∙2MeOH). Under the same conditions, the tungsten analogue (nBu4N)2[W3S7Br6] is completely or partly destroyed to give the complex (Ph4P)(Et3NH)[WO2(Tbc)2] (II). The structures of Ia·2MeOH and II were established by X-ray diffraction analysis (CCDC nos. 2213900 and 2213901, respectively). The redox properties of complex Ia and related (Ph4P)2[Mo3S7(Tbc)3] (Ib) and (Ph4P)2[Mo3S7(Tcc)3] (Ic) (Tcc is tetrachlorocatecholate) were also studied by cyclic voltammetry.