文摘
Carbenes are known for their ability to abstract HCl from hydrochlorosilanes to form carbene hydrochloride adducts. In contrast, the Si–H bond insertion products RSiCl<sub>2sub>(cAACH) (<b>2b>, <b>4b>, <b>6b>, and <b>8b>) have been formed in the reaction of RSiHCl<sub>2sub> [R = Ar(SiMe<sub>3sub>)N (<b>1b>), Cp* (<b>3b>), PhC(NtBu)<sub>2sub> (<b>5b>), Cl (<b>7b>); Ar = 2,6-iPr<sub>2sub>C<sub>6sub>H<sub>3sub>] with a cyclic alkyl(amino) carbene (cAAC:) irrespective of the steric demand of the R group. The new products have been characterized by various analytical tools including X-ray crystallography, electron ionization mass spectrometry, and NMR spectroscopy. Theoretical investigations have also been performed to understand why cAAC prefers insertion into the Si–H bond rather than the dehydrohalogenation pathway.