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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

Mears, Kristian L. Nguyen, Gia-Ann Ruiz, Bronson Lehmann, Annika Nelson, Jonah Fettinger, James C. Tuononen, Heikki M. Power, Philip P.

Format

Articles Research article

Published

2024

Series

Journal of the American Chemical Society

Subjects

activation energy

anions

bismuth

hydrocarbons

hydrogen

vety

hiilivedyt

vismutti

anionit

Publication in research information system

https://converis.jyu.fi/converis/portal/detail/Publication/197647025

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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