The reaction of metal carbonyl compounds with group 6 and 8 metallaboranes led us to report the synthesis and structural characterization of several novel mixed-metal chalcogenide tetrahedral clusters. Thermolysis of arachno-[(Cp∗RuCO)2B2H6], 1 and [Os3(CO)12] in the presence of 2-methylthiophene yielded [Cp∗Ru(CO)2(μ-H){Os3(CO)9}S], 3 and [Cp∗Ru(μ-H){Os3(CO)11}], 4. In a similar fashion, the reaction of [(Cp∗Mo)2B5H9], 2, with [Ru3(CO)12] and 2-methylthiophene yielded [Cp∗Ru(CO)2(μ-H){Ru3(CO)9}S], 5 and conjuncto-[(Cp∗Mo)2B5H8(μ-H){Ru3(CO)9}S], 6. Both compounds 3 and 5 can be described as 50-cve (cluster valence electron) mixed-metal chalcogenide clusters, in which a sulfur atom replaces one of the vertices of the tetrahedral core. Compounds 3 and 5 possess a [M3S] tetrahedral core, in which the sulfur is attached to an exo-metal fragment, unique in the [M3S] metal chalcogenide tetrahedral arrangements. All the compounds have been characterized by mass spectrometry, IR and 1H, 11B and 13C NMR spectroscopy in solution and the solid state structures were unequivocally established by crystallographic analysis of compounds 3, 5 and 6. © 2014 the Partner Organisations.