Hydrobismuthation : Insertion of Unsaturated Hydrocarbons into the Heaviest Main Group Element Bond to Hydrogen
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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2024Discipline
Epäorgaaninen kemiaNanoscience CenterEpäorgaaninen ja analyyttinen kemiaInorganic ChemistryNanoscience CenterInorganic and Analytical ChemistryCopyright
© 2024 the Authors
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.
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The content of the publication reflects only the author’s view. The funder is not responsible for any use that may be made of the information it contains.
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United States National Science Foundation Grant Nos. CHE-2152760 and CHE-1531193. European Research Council, Horizon 2020 Programme Grant No. 772510.License
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