Bussoli Guido, Boccalini Alberto, Bortoluzzi Marco, Cesari Cristiana, Iapalucci Maria Carmela, Funaioli Tiziana, Scorzoni Giorgia, Zacchini Stefano, Ruggieri Silvia, Femoni Cristina
Department of Industrial Chemistry "Toso Montanari", University of Bologna, Via Gobetti 85, 40129 Bologna, Italy.
Department of Molecular Sciences and Nanosystems, Ca' Foscari University of Venice, Via Torino 155, 30170 Mestre, VE, Italy.
Nanoscale. 2024 Oct 3;16(38):17852-17867. doi: 10.1039/d4nr02922d.
In this paper we present the investigation of the reactivity of [Rh(CO)] with InCl, with the aim of expanding the more general study that allowed us to obtain, among other species, the icosahedral [RhE(CO)] ( = 4 when E = Ge or Sn; = 3 when E = Sb or Bi) family of clusters. Indeed, the study resulted in the isolation and characterization of the analogous In-centred icosahedral [RhIn(CO)] nanocluster (1), which is isoelectronic and isostructural with the [RhE(CO)] congeners. During the course of the reaction two more new species, namely the octahedral [Rh(CO)InCl] (2) and the dimeric [{Rh(CO)InCl}] (3) have also been identified. The reaction between [Rh(CO)] and InCl 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, [Rh(CO)InCl] can be more selectively prepared by reacting either [Rh(CO)] or, less efficiently, [Rh(CO)] with InCl. As for the dimeric [{Rh(CO)InCl}] species, this was only isolated by carrying out the reaction with [Rh(CO)] 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 [RhIn(CO)] species was also analysed by EDS SEM, and further investigated through infrared spectroelectrochemistry and CV experiments to check its multivalence nature. Indeed, [RhIn(CO)] can reversibly undergo two monoelectronic oxidation and one bi-electronic reduction processes, behaving like an electron sponge and, thus, giving rise to the further [RhIn(CO)] derivatives ( = 1, 2 and 5). These results parallel the findings for the [RhE(CO)] series. The geometry variations of the metal framework associated with the changes in the cluster negative charge were investigated by means of DFT calculations.
在本文中，我们展示了对[Rh(CO)]与InCl反应活性的研究，目的是扩展更全面的研究，该研究使我们能够获得除其他物种外的二十面体[RhE(CO)]（当E = Ge或Sn时， = 4；当E = Sb或Bi时， = 3）簇家族。实际上，该研究导致分离并表征了类似的以In为中心的二十面体[RhIn(CO)]纳米簇（1），它与[RhE(CO)]同系物等电子且同结构。在反应过程中，还鉴定出另外两个新物种，即八面体[Rh(CO)InCl]（2）和二聚体[{Rh(CO)InCl}]（3）。事实证明，[Rh(CO)]与InCl之间的反应选择性很差；然而，通过微调一些反应参数，可以使反应更倾向于生成某一种产物。或者，[Rh(CO)InCl]可以通过使[Rh(CO)]或效率较低的[Rh(CO)]与InCl反应更有选择性地制备。至于二聚体[{Rh(CO)InCl}]物种，它仅通过在惰性气氛下而不是在CO气氛下与[Rh(CO)]反应来分离。所有簇均通过红外光谱和电喷雾质谱进行表征，其分子结构通过单晶X射线衍射研究完全确定。[RhIn(CO)]物种还通过能谱仪 扫描电子显微镜进行了分析，并通过红外光谱电化学和循环伏安实验进一步研究以检查其多价性质。实际上，[RhIn(CO)]可以可逆地经历两个单电子氧化和一个双电子还原过程，表现得像一个电子海绵，从而产生进一步的[RhIn(CO)]衍生物（ = 1、2和5）。这些结果与[RhE(CO)]系列的发现相似。通过密度泛函理论计算研究了与簇负电荷变化相关的金属骨架的几何变化。
