Efficient and Selective Hydrosilylation of Secondary and Tertiary Amides Catalyzed by an Iridium(III) Metallacycle: Development and Mechanistic Investigation

Readily accessible cationic IrIII metallacycles catalyze efficiently the chemoselective hydrosilylation of tertiary and secondary amides to amines. The catalyst described herein operates at low loadings using inexpensive 1,1,3,3‐tetramethyldisiloxane and allows fast reactions with high yields, selectivities, and turnover numbers. A transient iminium intermediate has been observed for the first time by using mass spectrometry, and the activation of the catalyst and the silane reagent have been studied by using DFT calculations. These fundamental insights support the present and future improvements of IrIII metallacycles through proper ligand modifications and enable further broad applications of catalysts based on metallacycles. Hydrosilylation of amides: Cationic IrIII metallacycle complexes are highly active catalysts for the chemoselective reduction of amides to amines through hydrosilylation reactions. A transient iminium intermediate is observed for the first time by using mass spectrometry. The activation of the catalyst and the silane reagent are studied by using DFT calculations.