Alkali-metal-supported bismuth polyhedra - principles and theoretical studies

• Verfasst von: Monakhov, Kirill [VerfasserIn]
• Verfasst von: Linti, Gerald W. [VerfasserIn]
• Verfasst von: Wolters, Lando P. [VerfasserIn]
• Verfasst von: Bickelhaupt, F. Matthias [VerfasserIn]
• Titel: Alkali-metal-supported bismuth polyhedra - principles and theoretical studies
• Verf.angabe: Kirill Yu. Monakhov, Gerald Linti, Lando P. Wolters, and F. Matthias Bickelhaupt
• E-Jahr: 2011
• Jahr: 25 May 2011
• Umfang: 8 S.
• Fussnoten: Gesehen am 07.09.2022
• Titel Quelle: Enthalten in: Inorganic chemistry
• Ort Quelle: Washington, DC : American Chemical Society, 1962
• Jahr Quelle: 2011
• Band/Heft Quelle: 50(2011), 12, Seite 5755-5762
• ISSN Quelle: 1520-510X
• DOI: doi:10.1021/ic200596c
• Datenträger: Online-Ressource
• Sprache: eng
• K10plus-PPN: 1815944366

Abstract

We have quantum chemically investigated the structure, stability, and bonding mechanism in highly aggregated alkali-metal salts of bismuthanediide anions [RBi]2- using relativistic density functional theory (DFT, at ZORA-BP86/TZ2P) in combination with a quantitative energy decomposition analysis (EDA). Our model systems are alkali-metal-supported bismuth polyhedra [(RBi)nM2n-4]4- with unique interpenetrating shells of a bismuth polyhedron and an alkali-metal superpolyhedron. Furthermore, we have analyzed the trianionic inclusion complexes [M′@{(RBi)nM2n-4}]3- involving an additional endohedral alkali-metal ion M′. The main objective is to assist the further development of synthetic approaches toward this class of compounds. Our analyses led to electron-counting rules relating, for example, the number of bonding orbitals (Nbond) of the cage molecules [(RBi)nM2n+Q]Q to the number of bismuth atoms (nBi), alkali-metal atoms (nM), and net charge Q as Nbond = nBi + nM - Q (R = one-electron donor ligand; M = alkali metal; n = 4-12; Q = −4, −6, −8). Finally, on the basis of our findings, we predict the next members in the 5-fold symmetrical row of alkali-metallobismaspheres with a macroicosahedral arrangement.