In this paper we present the investigation of the reactivity of [Rh7(CO)16]3− with InCl3, with the aim of expanding the more general study that allowed us to obtain, among other species, the icosahedral [Rh12E(CO)27]n (n = 4 when E = Ge or Sn; n = 3 when E = Sb or Bi) family of clusters. Indeed, the study resulted in the isolation and characterization of the analogous In-centred icosahedral [Rh12In(CO)28]3− nanocluster (1), which is isoelectronic and isostructural with the [Rh12E(CO)27]n congeners. During the course of the reaction two more new species, namely the octahedral [Rh6(CO)15InCl3]2− (2) and the dimeric [{Rh6(CO)15InCl2}2]2− (3) have also been identified. The reaction between [Rh7(CO)16]3− and InCl3 proved to be poorly selective; nevertheless, by fine tuning some reaction parameters it was possible to drive the reaction more towards one product or the other. Alternatively, [Rh6(CO)15InCl3]2− can be more selectively prepared by reacting either [Rh5(CO)15] or, less efficiently, [Rh6(CO)15]2- with InCl3. As for the dimeric [{Rh6(CO)15InCl2}2]2− species, this was only isolated by carrying out the reaction with [Rh7(CO)16]3− under inert atmosphere, as opposed to under CO. All clusters were characterized by IR spectroscopy and ESI-MS, and their molecular structures were fully established by single-crystal X-ray diffraction studies. The [Rh12In(CO)28]3− species was also analysed by EDS via SEM, and further investigated through in situ infrared spectroelectrochemistry and CV experiments to check its multivalence nature. Indeed, [Rh12In(CO)28]3− can reversibly undergo two monoelectronic oxidation and one bi-electronic reduction processes, behaving like an electron sponge and, thus, giving rise to the further [Rh12In(CO)28]n− derivatives (n = 1, 2 and 5). These results parallel the findings for the [Rh12E(CO)27]n series. The geometry variations of the metal framework associated to the changes in the cluster negative charge were investigated by means of DFT calculations.

Guido Bussoli, A.B. (2024). Atomically Precise Rhodium-Indium Carbonyl Nanoclusters: Synthesis, Characterization, Crystal Structure and Electron-Sponge Features. NANOSCALE, 16, 17852-17867 [10.1039/d4nr02922d].

Atomically Precise Rhodium-Indium Carbonyl Nanoclusters: Synthesis, Characterization, Crystal Structure and Electron-Sponge Features

Guido Bussoli;Cristiana Cesari;Maria Carmela Iapalucci;Giorgia Scorzoni;Stefano Zacchini;Cristina Femoni
2024

Abstract

In this paper we present the investigation of the reactivity of [Rh7(CO)16]3− with InCl3, with the aim of expanding the more general study that allowed us to obtain, among other species, the icosahedral [Rh12E(CO)27]n (n = 4 when E = Ge or Sn; n = 3 when E = Sb or Bi) family of clusters. Indeed, the study resulted in the isolation and characterization of the analogous In-centred icosahedral [Rh12In(CO)28]3− nanocluster (1), which is isoelectronic and isostructural with the [Rh12E(CO)27]n congeners. During the course of the reaction two more new species, namely the octahedral [Rh6(CO)15InCl3]2− (2) and the dimeric [{Rh6(CO)15InCl2}2]2− (3) have also been identified. The reaction between [Rh7(CO)16]3− and InCl3 proved to be poorly selective; nevertheless, by fine tuning some reaction parameters it was possible to drive the reaction more towards one product or the other. Alternatively, [Rh6(CO)15InCl3]2− can be more selectively prepared by reacting either [Rh5(CO)15] or, less efficiently, [Rh6(CO)15]2- with InCl3. As for the dimeric [{Rh6(CO)15InCl2}2]2− species, this was only isolated by carrying out the reaction with [Rh7(CO)16]3− under inert atmosphere, as opposed to under CO. All clusters were characterized by IR spectroscopy and ESI-MS, and their molecular structures were fully established by single-crystal X-ray diffraction studies. The [Rh12In(CO)28]3− species was also analysed by EDS via SEM, and further investigated through in situ infrared spectroelectrochemistry and CV experiments to check its multivalence nature. Indeed, [Rh12In(CO)28]3− can reversibly undergo two monoelectronic oxidation and one bi-electronic reduction processes, behaving like an electron sponge and, thus, giving rise to the further [Rh12In(CO)28]n− derivatives (n = 1, 2 and 5). These results parallel the findings for the [Rh12E(CO)27]n series. The geometry variations of the metal framework associated to the changes in the cluster negative charge were investigated by means of DFT calculations.
2024
Guido Bussoli, A.B. (2024). Atomically Precise Rhodium-Indium Carbonyl Nanoclusters: Synthesis, Characterization, Crystal Structure and Electron-Sponge Features. NANOSCALE, 16, 17852-17867 [10.1039/d4nr02922d].
Guido Bussoli, Alberto Boccalini, Marco Bortoluzzi, Cristiana Cesari, Maria Carmela Iapalucci, Tiziana Funaioli, Giorgia Scorzoni, Stefano Zacchini, S...espandi
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11585/983875
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