B(C₆F₅)₃-Catalyzed Selective Chlorination of Hydrosilanes

The chlorination of Si−H bonds often requires stoichiometric amounts of metal salts in conjunction with hazardous reagents, such as tin chlorides, Cl₂, and CCl₄. The catalytic chlorination of silanes often involves the use of expensive transition-metal catalysts. By a new simple, selective, and highly efficient catalytic metal-free method for the chlorination of Si−H bonds, mono-, di-, and trihydrosilanes were selectively chlorinated in the presence of a catalytic amount of B(C₆F₅)₃ or Et₂O⋅B(C₆F₅)₃ and HCl with the release of H₂ as a by-product. The hydrides in di- and trihydrosilanes could be selectively chlorinated by HCl in a stepwise manner when Et₂O⋅B(C₆F₅)₃ was used as the catalyst. A mechanism is proposed for these catalytic chlorination reactions on the basis of competition experiments and density functional theory (DFT) calculations.