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

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 .

Exploring Spin‐Orbit Effects in a [Cu6Tl]+ Nanocluster Featuring an Uncommon Tl−H Interaction

“…Heavy element main group hydrides have proven to be fertile ground for studying relativistic effects. [1][2][3][4][5][6][7][8][9] These effects can be easily observed by 1 H NMR spectroscopy. [10][11][12] For example, the lead hydride [Ar*PbH] 2 (Ar* = 2,6-(C 6 H 2 -2,4,6-i Pr 3 ) 2 C 6 H 3 ) exhibits a hydride resonance of 35.6 ppm.…”