SYNTHESIS, STRUCTURAL CHARACTERIZATION, AND MOLECULAR-ORGANIZATION IN THE SOLID-STATE OF [H2OS10C(CO)24]

The neutral dihydrido cluster [H2Os10C(CO)24] has been obtained from the protonation of the dianion [Os10C(CO)24]2- in MeCN with H2SO4 and, alternatively, from the thermolysis of [Os3(CO)12] in cyclohexane. The X-ray diffraction study of the black needles obtained from the latter reaction reveals a structure closely related to that of the carbido clusters [Os10C(CO)24]2- and [HOs10C(CO)24]- and to that of the tetrahydrido species [H4Os10(CO)24]2-. The X-ray analysis has afforded convincing evidence of the presence of two bridging H ligands on the surface of the Os10 metal frame and not, as previously suggested, in tetrahedral interstitial sites. A detailed examination of the molecular organization within the crystal lattice has been carried out by means of computer graphics and potential energy calculations.