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A series of new W-Co-S clusters have been synthesized utilizing the complex [Et4N][(Tp*)WS3] (Tp* = hydridotris(3,5-dimethylpyrazol-1-yl)borate(1-)) as the synthetic template, by rational control of the stoichiometry of reactants and by employment of a reductant or precipitant as an auxiliary reagent. By solubility control or addition of a precipitant to avoid the involvement of Cl- in the reaction, the cluster [(Tp*)WS3]2Co (2) could be obtained. With different ratios of the Co source to the template, together with the use of an approp