Stabilization of Reactive Nitrene by Silylenes without Using a Reducing Metal
| Autor: | Samir Kumar Sarkar, Shahila Muhammed, Daniel Lüert, Pattiyil Parameswaran, Mohd Nazish, Dietmar Stalke, Zhi Yang, Paul Niklas Ruth, Christina M. Legendre, Herbert W. Roesky, Regine Herbst-Irmer, Yi Ding |
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| Rok vydání: | 2021 |
| Předmět: |
010405 organic chemistry
Nitrene Silylene General Medicine General Chemistry 010402 general chemistry Ring (chemistry) 01 natural sciences Catalysis 0104 chemical sciences 3. Good health chemistry.chemical_compound chemistry Yield (chemistry) Reagent Polymer chemistry Molecular orbital Trifluoromethanesulfonate Lone pair |
| Zdroj: | Angewandte Chemie International Edition. 60:27206-27211 |
| ISSN: | 1521-3773 1433-7851 |
| Popis: | 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)-SiI 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)-SiI 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. |
| Databáze: | OpenAIRE |
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