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The reactivity of [Rh7(CO)16]3– with SbCl3 has been deeply investigated with the aim of finding a new approach to prepare atomically precise metalloid clusters. In particular, by varying the stoichiometric ratios, the reaction atmosphere (carbon monoxide or nitrogen), the solvent, and by working at room temperature and low pressure, we were able to prepare two large carbonyl clusters of nanometer size, namely, [Rh20Sb3(CO)36]3– and [Rh21Sb2(CO)38]5–. A third large species composed of 28 metal atoms was isolated, but its exact formulation in terms of metal stoichiometry could not be incontrovertibly confirmed. We also adopted an alternative approach to synthesize nanoclusters, by decomposing the already known [Rh12Sb(CO)27]3– species with PPh3, willing to generate unsaturated fragments that could condense to larger species. This strategy resulted in the formation of the lower-nuclearity [Rh10Sb(CO)21PPh3]3– heteroleptic cluster instead. All three new compounds were characterized by IR spectroscopy, and their molecular structures were fully established by single-crystal X-ray diffraction studies. These showed a distinct propensity for such clusters to adopt an icosahedral-based geometry. Their characterization was completed by ESI-MS and NMR studies. The electronic properties of the high-yield [Rh21Sb2(CO)38]5– cluster were studied through cyclic voltammetry and in situ infrared spectroelectrochemistry, and the obtained results indicate a multivalent nature., The reactivity of [Rh7(CO)16]3− with SbCl3 has been deeply investigated as a new approach to prepare atomically precise metal nanoparticles. By varying the reaction conditions, we obtained three large carbonyl nanoclusters, [Rh20Sb3(CO)36]3−, [Rh21Sb2(CO)38]5−, and [Rh28−xSbx(CO)44]6−, and the lower-nuclearity [Rh10Sb(CO)21PPh3]3− species. They have all been characterized through X-ray diffraction, IR spectroscopy, and other techniques based on their specific nature. Spectroelectrochemical studies on [Rh21Sb2(CO)38]5− unravelled its multivalent nature.

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.

The reaction of [Rh