Stabilization of Reactive Nitrene by Silylenes without Using a Reducing Metal

Herein, we report the stabilization of nitrene reagents as the source of a nitrogen atom to synthesize nitrogen‐incorporated R(1)LSi‐N←SiLR(2) (1) [L=PhC(NtBu)(2); R(1)=NTMS(2), R(2)=NTMS]. Compound 1 is synthesized by reacting LSi(I)‐Si(I)L with 3.1 equivalents of Me(3)SiN(3) at low temperature to afford a triene‐like structural framework. Whereas the reaction of the LSi(I)‐Si(I)L with 2.1 equivalents of Me(3)SiN(3) at room temperature produced silaimine 2 with a central four‐membered Si(2)N(2) ring which is accompanied by a silylene LSi and a cleaved silylene fragment. 1 further reacts with AgOTf at room temperature to yield compound 3 which shows coordination of nitrene to silver with the triflate salt. The compounds 1 and 2 were fully characterized by NMR, mass spectrometry, and X‐ray crystallographic analysis. The quantum mechanical calculations reveal that compounds 1 and 2 have dicoordinated monovalent N atoms having two active lone pairs of electrons. These lone pairs are stabilized by hyperconjugative interactions.