Interstitial Bismuth Atoms in Icosahedral Rhodium Cages: Syntheses, Characterizations, and Molecular Structures of the [Bi@Rh12(CO)27](3-), [(Bi@Rh12(CO)26)2Bi](5-), [Bi@Rh14(CO)27Bi2](3-), and [Bi@Rh17(CO)33Bi2](4-) Carbonyl Clusters.

Author(s) Femoni, C.; Bussoli, G.; Ciabatti, I.; Ermini, M.; Hayatifar, M.; Iapalucci, M.C.; Ruggieri, S.; Zacchini, S.
Journal Inorg Chem
Date Published 2017 Jun 05

The reaction of [Rh7(CO)16](3-) with BiCl3 under N2 and at room temperature results in the formation of the new heterometallic [Bi@Rh12(CO)27](3-) cluster in high yields. Further controlled addition of BiCl3 leads first to the formation of the dimeric [(Bi@Rh12(CO)26)2Bi](5-) and the closo-[Bi@Rh14(CO)27Bi2](3-) species in low yields, and finally, to the [Bi@Rh17(CO)33Bi2](4-) cluster. All clusters were spectroscopically characterized by IR and electrospray ionization mass spectrometry, and their molecular structures were fully determined by X-ray diffraction studies. Notably, they represent the first examples of Bi atoms interstitially lodged in metallic cages that, in this specific case, are all based on an icosahedral geometry. Moreover, [Bi@Rh14(CO)27Bi2](3-) forms an exceptional network of infinite zigzag chains in the solid state, thanks to intermolecular Bi-Bi distances.

DOI 10.1021/acs.inorgchem.7b00409
ISSN 1520-510X
Citation Inorg Chem. 2017;56(11):63436351.

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