Chemistry - A European Journal · 2018 · 16 citations · 53 references
A preparatively facile, highly selective synthesis of bifunctional monosilanes R<sub>2</sub> SiHCl, RSiHCl<sub>2</sub> and RSiH<sub>2</sub> Cl is reported. By chlorination of R<sub>2</sub> SiH<sub>2</sub> and RSiH<sub>3</sub> with concentrated HCl/ether solutions, the stepwise introduction of Si-Cl bonds is readily controlled by temperature and reaction time for a broad range of substrates. In a combined experimental and computational study, we establish a new mode of Si-H bond activation assisted by Lewis bases such as ethers, amines, phosphines, and chloride ions. Elucidation of the underlying reaction mechanisms shows that alcohol assistance through hydrogen-bond networks is equally efficient and selective. Remarkably, formation of alkoxysilanes or siloxanes is not observed under moderate reaction conditions.
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