Two new disubstituted derivatives of the clusters Rh₆(CO) ₁₆ and H₄Ru₄(CO)₁₂ with the heterobidentate ligand [Ph₂P(2-CH₃SC₆H ₄)] were synthesized. Structures of these compounds were completely characterized both in solid phase and solution. The H₄Ru ₄(CO)₁₀[k²(P,S)-Ph₂P(2-CH ₃SC₆H₄)] cluster is an example of a structure, in which a chelating coordination of a heterobidentate ligand results in the occurrence of a center of asymmetry associated with the substituted metal atom. This type of polynuclear complexes is of interest for obtaining essentially new catalysts for asymmetric synthesis on the basis of cluster compounds.