Hydrobismuthation: Insertion of Unsaturated Hydrocarbons into the Heaviest Main Group Element Bond to Hydrogen

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

doi:10.1021/jacs.3c06535

Hydrobismuthation: Insertion of Unsaturated Hydrocarbons into the Heaviest Main Group Element Bond to Hydrogen

J Am Chem Soc. 2024 Jan 10;146(1):19-23. doi: 10.1021/jacs.3c06535. Epub 2024 Jan 2.

Authors

Kristian L Mears¹, Gia-Ann Nguyen¹, Bronson Ruiz¹, Annika Lehmann², Jonah Nelson^{2

3}, James C Fettinger¹, Heikki M Tuononen², Philip P Power¹

Affiliations

¹ Department of Chemistry, University of California, One Shields Avenue, Davis, California 95616, United States.
² Department of Chemistry, NanoScience Centre, University of Jyväskylä, P.O. Box 35, FI-40140 Jyväskylä, Finland.
³ Department of Chemistry, University of Calgary, 2500 University Drive N.W., Calgary, Alberta, Canada, T2N 1N4.

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.