Abstract The metal‐free catalytic hydrogenolysis of silyl triflates and halides (I, Br) to hydrosilanes is unlocked by using arylborane Lewis acids as catalysts. In the presence of a nitrogen base, the catalyst acts as a Frustrated Lewis Pair (FLP) able to split H2 and generate a boron hydride intermediate capable of reducing (pseudo)halosilanes. This metal‐free organocatalytic system is competitive with metal‐based catalysts and enables the formation of a variety of hydrosilanes at room temperature in high yields (>85?%) under a low pressure of H2 (≤10?bar).
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