Selective Silylation of Nitriles with an NHC-Stabilized Silylene to 1,2-Disilylimines and Subsequent Synthesis of Silaaziridines

The highly regioselective synthesis of trans-1,2-disilylimines have been achieved by the bis-silylation of nitriles with the NHC-stabilized silylene NHC-Si­(NArSiMe3)Cl (1; Ar = 2,6-iPr2C6H3, NHC = 1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene). The bis-silylation involves the migration of the SiMe3 group on the nitrogen atom in the silylene to the carbon atom of the nitrile functionality. The 1,2-disilylimine products feature an NHC-stabilized silaimine moiety and could undergo nucleophilic attack by phenyllithium reagents to yield novel silaaziridines with an NHC-stabilized exocyclic SiN double bond.