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

Inorganic Chemistry
Cristina FemoniStefano Zacchini

Abstract

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.

References

Jul 5, 2006·Angewandte Chemie·Jose M Goicoechea, Slavi C Sevov
Sep 26, 2007·Dalton Transactions : an International Journal of Inorganic Chemistry·Cristina FemoniJonathan A Iggo
Jan 11, 2008·Journal of the American Chemical Society·Manzhou ZhuRongchao Jin
Jun 3, 2010·Journal of the American Chemical Society·Huifeng QianRongchao Jin
Sep 6, 2013·Nature·Anil DesireddyTerry P Bigioni
Jul 30, 2014·Angewandte Chemie·Sandra García-Gallego, Gonçalo J L Bernardes

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