The derivatives of the H2RuOs3(CO)13 and H4Ru4(CO)12 carbonylhydride clusters containing functionalized (including chiral) phosphines were synthesized. The solid-state structure of H2RuOs3(CO)12(Ph 2P(C4H3S)) was determined by X-ray diffraction analysis. The structures of other compounds in solution were determined using IR and 1H and 31P NMR spectroscopy. A study of the temperature dependences of the 1H NMR spectra of the phosphine-substituted tetrahedral clusters along with the analysis of literature data for their analogs showed that compounds of this type exist in solution as an equilibrium mixture of isomers, which differ in arrangement of the hydride ligands at the cluster skeleton. Interconversion of the isomeric forms is due to migration of the hydride ligands over the cluster skeleton. A general model for this dynamic process was proposed. The model is consistent with both our data and earlier results of other authors.
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