Hydrobismuthation : Insertion of Unsaturated Hydrocarbons into the Heaviest Main Group Element Bond to Hydrogen
Abstract
The bismuth hydride (2,6-Mes2H3C6)2BiH (1, Mes = 2,4,6-trimethylphenyl), which has a Bi–H 1H NMR spectroscopic signal at δ = 19.64 ppm, was reacted with phenylacetylene at 60 °C in toluene to yield [(2,6-Mes2C6H3)2BiC(Ph)=CH2] (2) after 15 min. Compound 2 was characterized by 1H, 13C NMR, and UV–vis spectroscopy, single crystal X-ray crystallography, and calculations employing density functional theory. Compound 2 is the first example of a hydrobismuthation addition product and displays Markovnikov regioselectivity. Computational methods indicated that it forms via a radical mechanism with an associated Gibbs energy of activation of 91 kJ mol–1 and a reaction energy of −90 kJ mol–1.
Main Authors
Format
Articles
Research article
Published
2024
Series
Subjects
Publication in research information system
Publisher
American Chemical Society (ACS)
The permanent address of the publication
https://urn.fi/URN:NBN:fi:jyu-202401121265Use this for linking
Review status
Peer reviewed
ISSN
0002-7863
DOI
https://doi.org/10.1021/jacs.3c06535
Language
English
Published in
Journal of the American Chemical Society
Citation
- Mears, K. L., Nguyen, G.-A., Ruiz, B., Lehmann, A., Nelson, J., Fettinger, J. C., Tuononen, H. M., & Power, P. P. (2024). Hydrobismuthation : Insertion of Unsaturated Hydrocarbons into the Heaviest Main Group Element Bond to Hydrogen. Journal of the American Chemical Society, 146(1), 19-23. https://doi.org/10.1021/jacs.3c06535
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Funder(s)
European Commission
Funding program(s)
ERC Consolidator Grant
ERC Consolidator Grant
Funded by the European Union. Views and opinions expressed are however those of the author(s) only and do not necessarily reflect those of the European Union or the European Education and Culture Executive Agency (EACEA). Neither the European Union nor EACEA can be held responsible for them.
Additional information about funding
United States National Science Foundation Grant Nos. CHE-2152760 and CHE-1531193. European Research Council, Horizon 2020 Programme Grant No. 772510.
Copyright© 2024 the Authors