Bismuth Cations: Fluoride Ion Abstraction, Isocyanide Coordination, and Impact of Steric Bulk on Lewis Acidity

Bismuth Cations: Fluoride Ion Abstraction, Isocyanide Coordination, and Impact of Steric Bulk on Lewis Acidity

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 invest...

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Bibliographic Details
Main Authors: Dunaj, Tobias, Schwarzmann, Johannes, Ramler, Jacqueline, Stoy, Andreas, Reith, Sascha, Nitzsche, Joel, Völlinger, Lena, Hänisch, Carsten von, Lichtenberg, Crispin
Format: Article
Language:English
Published: Philipps-Universität Marburg 2023
Subjects:
Chemie
Chemistry & allied sciences
Online Access:PDF Full Text
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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.
Physical Description:12 Pages
DOI:10.1002/chem.202204012

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