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 R₁ LSi-N←SiLR₂ (1) [L=PhC(NtBu)₂ ; R₁ =NTMS₂ , R₂ =NTMS]. Compound 1 is synthesized by reacting LSi(I)-Si^I L with 3.1 equivalents of Me₃ SiN₃ 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 Me₃ SiN₃ at room temperature produced silaimine 2 with a central four-membered Si₂ N₂ 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.