4.8 Article

Metal-Free Catalytic Hydrogenolysis of Silyl Triflates and Halides into Hydrosilanes

Journal

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 61, Issue 23, Pages -

Publisher

WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202200911

Keywords

Frustrated Lewis Pair; H-2 Activation; Hydrogenolysis; Hydrosilane Synthesis; Metal-Free

Funding

  1. CEA
  2. CNRS
  3. University Paris-Saclay
  4. European Research Council (ERC) [818260]
  5. CINES [A0100806494]

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The metal-free catalytic hydrogenolysis of silyl triflates and halides to hydrosilanes is achieved using arylborane Lewis acids as catalysts. The catalyst acts as a Frustrated Lewis Pair and is able to split H-2 and generate a boron hydride intermediate capable of reducing (pseudo)halosilanes. This metal-free organocatalytic system competes with metal-based catalysts and enables the formation of a variety of hydrosilanes at room temperature in high yields under low hydrogen pressure.
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 H-2 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 H-2 (<= 10 bar).

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