Abstract
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).