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
Abstract
High Resolution Image Download MS PowerPoint Slide The bismuth hydride (2,6-Mes 2 H 3 C 6 ) 2 BiH ( 1, Mes = 2,4,6-trimethylphenyl), which has a Bi–H 1 H NMR spectroscopic signal at δ = 19.64 ppm, was reacted with phenylacetylene at 60 °C in toluene to yield [(2,6-Mes 2 C 6 H 3 ) 2 BiC(Ph)=CH 2 ] ( 2 ) after 15 min. Compound 2 was characterized by 1 H, 13 C 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 .