Reactions of labile Os₃(CO)₁₀(NCMe)₂ and Rh₆(CO)₁₅(NCMe) clusters and dinuclear Rh ₂(CO)₄Cl₂ complex with chiral (S)-[2-(4-isopropyl-4,5-dihydro-1,3-oxazol-2-yl)phenyl]di(1H-pyrrol-1-yl) phosphine were studied. The reaction of Os₃(CO)₁₀(NCMe) ₂ with the chiral phosphine was diastereoselective, and it afforded only one diastereoisomer with ee 100%. All isolated compounds were completely characterized by NMR and mass spectra and X-ray diffraction data.