Alkali-metal-supported bismuth polyhedra - principles and theoretical studies
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 (ED...
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| Hauptverfasser: | , , , |
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| Dokumenttyp: | Article (Journal) |
| Sprache: | Englisch |
| Veröffentlicht: |
25 May 2011
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Inorganic chemistry
Year: 2011, Jahrgang: 50, Heft: 12, Pages: 5755-5762 |
| ISSN: | 1520-510X |
| DOI: | 10.1021/ic200596c |
| Online-Zugang: | Verlag, lizenzpflichtig, Volltext: https://doi.org/10.1021/ic200596c
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| Verfasserangaben: | Kirill Yu. Monakhov, Gerald Linti, Lando P. Wolters, and F. Matthias Bickelhaupt |
| Zusammenfassung: | 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. |
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| Beschreibung: | Gesehen am 07.09.2022 |
| Beschreibung: | Online Resource |
| ISSN: | 1520-510X |
| DOI: | 10.1021/ic200596c |