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BIT’s major progress in nitrene

News Resource: School of Chemistry and Chemical Engineering

Editor: News Agency of BIT

Translator: Han Miaomiao, News Agency of BIT

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Recently, Professor Yang Zhi from the School of Chemistry and Chemical Engineering of Beijing Institute of Technology and his collaborators have made important progress in the field of nitrene. Related results, published in the top international chemistry journal Angewandte Chemie International Editiowith the title of  "Stabilization of Reactive Nitrene by Silylenes without using a Reducing Metal" and it was listed as Hot Paper by the journal. Ding Yi, Ph.D. from the School of Chemistry and Chemical Engineering, BIT, is the first author. Professor Yang Zhi from BIT, Professor Herbert W. Roesky and Dietmar Stalke from the University of Göttingen, and Dr Pattyyil Parameswaran from the National Institute of Technology Calicut are the Co-corresponding author.

Nitrene is the nitrogen analogue of a carbene and has been used in many organic transformation reactions. The uncharged and univalent nitrogen atom in nitrene is highly reactive and was not isolated till now. The nitrene is generated in situ during reactions from its parent molecules such as azide or isocyanate by releasing N2 or CO, respectively. Whereas silylenes and bis(silylene)are the heavier analogues of carbenes and have attracted great interest over the last decade because of their easy synthesis. LSiCl and LSi-SiL were extensively studied by different groups in recent years owing to their unique bonding nature and reactivities.

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It is the first 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 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 Organic silver compound 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. The above studies put forward new reaction types and reaction mechanisms of silylene and nitrene, which are of great significance for understanding the reaction system and activation mechanism of carbene analogs.

Paper link: https://onlinelibrary.wiley.com/doi/10.1002/anie.202110456


Personal profile attached:

Professor Yang Zhi, the New Century Excellent Talent in the Ministry of Education, has been long researching in organometallic chemistry. He has published dozens of academic papers as the first or corresponding author. His representative papers include 4 papers on Angewandt Chemie Internation Edition, 2 papers on Journal of the American Chemical Society, 2 papers on Coordination Chemistry Review, 1 paper on Green Chemistry, etc.

Homepage: https://cce.bit.edu.cn/szll/ayjscz/hgxk/index.htm