Hastreiter, Florian and Lorenz, Corinna and Hioe, Johnny and Gaertner, Stefanie and Lokesh, Nanjundappa and Korber, Nikolaus and Gschwind, Ruth M. (2019) Elusive Zintl Ions [mu-HSi4](3-) and [Si-5](2-) in Liquid Ammonia: Protonation States, Sites, and Bonding Situation Evaluated by NMR and Theory. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 58 (10). pp. 3133-3137. ISSN 1433-7851, 1521-3773
Full text not available from this repository. (Request a copy)Abstract
The existence of [mu-HSi4](3-) in liquid ammonia solutions is confirmed by H-1 and Si-29 NMR experiments. Both NMR and quantum chemical calculations reveal that the H atom bridges two Si atoms of the [Si-4](4-) cluster, contrary to the expectation that it is located at one vertex Si of the tetrahedron. The calculations also indicate that in the formation of [mu-HSi4](3-), protonation is driven by a high charge density and an increase of electron delocalization compared to [Si-4](4-). Additionally, [Si-5](2-) was detected for the first time and characterized by NMR. Calculations show that it is resistant to protonation, owing to a strong charge delocalization, which is significantly reduced upon protonation. Thus, our methods reveal three silicides in liquid ammonia: unprotonated [Si-5](2-), terminally protonated [HSi9](3-), and bridge-protonated [mu-HSi4](3-). The protonation trend can be roughly predicted by the difference in charge delocalization between the parent compound and the product, which can be finely tuned by the presence of counter ions in solution.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | CRYSTAL-STRUCTURES; SILICON CLUSTERS; GROUP ELEMENTS; CHEMISTRY; ANIONS; PHOSPHORUS; SI-4(4-); Si-29 NMR; ELI-D analysis; NBO analysis; silicides; Zintl anions |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Anorganische Chemie > Arbeitskreis Prof. Dr. Nikolaus Korber Chemistry and Pharmacy > Institut für Organische Chemie > Arbeitskreis Prof. Dr. Ruth Gschwind |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 21 Apr 2020 06:38 |
| Last Modified: | 21 Apr 2020 06:38 |
| URI: | https://pred.uni-regensburg.de/id/eprint/27386 |
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