Dokument
| Titel: | Bismuth Cations: Fluoride Ion Abstraction, Isocyanide Coordination, and Impact of Steric Bulk on Lewis Acidity |
| Autor: | Dunaj, Tobias |
| Weitere Verfasser: | Schwarzmann, Johannes; Ramler, Jacqueline; Stoy, Andreas; Reith, Sascha; Nitzsche, Joel; Völlinger, Lena; Hänisch, Carsten von; Lichtenberg, Crispin |
| Veröffentlicht: | 2023 |
| URI: | https://archiv.ub.uni-marburg.de/es/2023/0071 |
| DOI: | https://doi.org/10.1002/chem.202204012 |
| URN: | urn:nbn:de:hebis:04-es2023-00717 |
| DDC: | 540 Chemie |
| Publikationsdatum: | 2023-07-10 |
| Lizenz: | https://creativecommons.org/licenses/by-nc-nd/4.0/ |
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Summary:
The molecular compound [BiDipp2(SbF6)], containing the bulky, donor-free bismuth cation [BiDipp2]+ has been synthesized and fully characterized (Dipp=2,6-iPr2-C6H3). Using its methyl analog [BiMe2(SbF6)] as a second reference point, the impact of steric bulk on bismuth-based Lewis acidity was investigated in a combined experimental (Gutmann-Beckett and modified Gutmann-Beckett methods) and theoretical approach (DFT calculations). Reactivity studies of the bismuth cations towards [PF6]− and neutral Lewis bases such as isocyanides C≡NR’ revealed facile fluoride ion abstraction and straightforward Lewis pair formation, respectively. The first examples of compounds featuring bismuth-bound isocyanides have been isolated and fully characterized.
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