Herein, we report the stabilization of nitrene reagents as the source of a nitrogen atom to synthesize nitrogen-incorporated R1LSi-N←SiLR2 (1) [L=PhC(NtBu)2; R1=NTMS2, R2=NTMS]. Compound 1 is synthesized by reacting LSi(I)-SiIL with 3.1 equivalents of Me3SiN3 at low temperature to afford a triene-like structural framework. Whereas the reaction of the LSi(I)-SiIL with 2.1 equivalents of Me3SiN3 at room temperature produced silaimine 2 with a central four-membered Si2N2 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.
CITATION STYLE
Ding, Y., Sarkar, S. K., Nazish, M., Muhammed, S., Lüert, D., Ruth, P. N., … Roesky, H. W. (2021). Stabilization of Reactive Nitrene by Silylenes without Using a Reducing Metal. Angewandte Chemie - International Edition, 60(52), 27206–27211. https://doi.org/10.1002/anie.202110456
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