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Metal Silylenes Generated by Double Silicon–Hydrogen Activation: Key Intermediates in the Rhodium-Catalyzed Hydrosilylation of Ketones


  • We thank the Deutsche Forschungsgemeinschaft (SFB 623) for funding and the Deutsch-Französische Hochschule (UFA) for support of this work.


Rhodium silylenes, which are generated by double Si–H activation at the metal, are involved in a low-activation-barrier mechanism of the hydrosilylation of ketones with R2SiH2. A DFT-based study of reaction mechanisms accounts for the experimental observations, notably the rate enhancement for R2SiH2 over R3SiH and an inverse kinetic isotope effect.

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