Stabilization of Reactive Nitrene by Silylenes without Using a Reducing Metal
Yi Ding, Samir Kumar Sarkar, Mohd Nazish, Shahila Muhammed, Daniel Lüert, Paul Niklas Ruth, Christina M. Legendre, Regine Herbst‐Irmer, Pattiyil Parameswaran, Dietmar Stalke, Zhi Yang, Herbert W. Roesky
Abstract
Abstract 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(N t Bu) 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.