Skip to main page content
U.S. flag

An official website of the United States government

Dot gov

The .gov means it’s official.
Federal government websites often end in .gov or .mil. Before sharing sensitive information, make sure you’re on a federal government site.

Https

The site is secure.
The https:// ensures that you are connecting to the official website and that any information you provide is encrypted and transmitted securely.

Access keys NCBI Homepage MyNCBI Homepage Main Content Main Navigation
. 2023 May 26;29(30):e202204012.
doi: 10.1002/chem.202204012. Epub 2023 Mar 31.

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

Tobias Dunaj  1 , Johannes Schwarzmann  1 , Jacqueline Ramler  1 , Andreas Stoy  1 , Sascha Reith  1 , Joel Nitzsche  1 , Lena Völlinger  1 , Carsten von Hänisch  1 , Crispin Lichtenberg  1
Affiliations

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

Tobias Dunaj et al. Chemistry. .

Abstract

The molecular compound [BiDipp2 (SbF6 )], containing the bulky, donor-free bismuth cation [BiDipp2 ]+ has been synthesized and fully characterized (Dipp=2,6-iPr2 -C6 H3 ). 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.

Keywords: Lewis acidity; Lewis pair formation; bismuth; cationic species.

PubMed Disclaimer

References

    1. C. Lichtenberg, Chem. Commun. 2021, 57, 4483-4495.
    1. M. Olaru, D. Duvinage, E. Lork, S. Mebs, J. Beckmann, Angew. Chem. Int. Ed. 2018, 57, 10080-10084;
    1. Angew. Chem. 2018, 130, 10237-10241.
    1. M. M. Siddiqui, S. K. Sarkar, M. Nazish, M. Morganti, C. Köhler, J. Cai, L. Zhao, R. Herbst-Irmer, D. Stalke, G. Frenking, H. W. Roesky, J. Am. Chem. Soc. 2021, 143, 1301-1306.
    1. J. Ramler, A. Stoy, T. Preitschopf, J. Kettner, I. Fischer, B. Roling, F. Fantuzzi, C. Lichtenberg, Chem. Commun. 2022, 58, 9826-9829.

LinkOut - more resources