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Article Dans Une Revue Chemistry - A European Journal Année : 2023

Metal‐Free Catalytic Hydrogenolysis of Chlorosilanes into Hydrosilanes with “Inverse” Frustrated Lewis Pairs

Résumé

The challenging metal‐free catalytic hydrogenolysis of silyl chlorides to hydrosilanes is unlocked by using an inverse frustrated Lewis pair (FLP), combining a mild Lewis acid (Cy 2 BCl) and a strong phosphazene base (BTPP) in mild conditions (10 bar of H 2 , r. t.). In the presence of a stoichiometric amount of the base, the hydrosilanes R 3 SiH (R=Me, Et, Ph) are generated in moderate to high yields (up to 95 %) from their chlorinated counterparts. A selective formation of the valuable difunctional monohydride Me 2 SiHCl is also obtained from Me 2 SiCl 2 . A mechanism is proposed based on stoichiometric experiments and DFT calculations; it highlights the critical role of borohydride species generated by the heterolytic splitting of H 2 .
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Origine : Publication financée par une institution
Licence : CC BY NC - Paternité - Pas d'utilisation commerciale

Dates et versions

hal-04236744 , version 1 (11-10-2023)

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Gabriel Durin, Jean‐claude Berthet, Pierre Thuéry, Emmanuel Nicolas, Thibault Cantat. Metal‐Free Catalytic Hydrogenolysis of Chlorosilanes into Hydrosilanes with “Inverse” Frustrated Lewis Pairs. Chemistry - A European Journal, 2023, 29 (61), ⟨10.1002/chem.202302155⟩. ⟨hal-04236744⟩
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