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重氮烯烃的分离与表征
作者:小柯机器人 发布时间:2021/10/9 13:28:39

瑞士洛桑联邦理工学院Severin Kay团队报道了重氮烯烃的分离与表征。相关研究成果发表在2021年10月7日出版的《自然—化学》。

重氮烯往往是高反应性化合物,迅速失去二氮。到目前为止,关于重氮烯烃的大多数实验证据都是通过诱捕实验间接获得的。

该文中,研究人员发现重氮烯烃是在N-杂环烯烃与一氧化二氮的反应中形成的。该产品得益于共振稳定,使得其在制备规模上进行分离,以及包括晶体学分析在内的综合表征。N-杂环重氮烯烃表现出很强的叶列特征,在重氮基附近的碳原子上具有很高的电荷密度。尽管存在末端N2基团,N-杂环重氮烯显示出良好的热稳定性,超过了大多数重氮烷。N-杂环重氮烯烃能在不释放二氮的情况下与过渡族和主族金属配合物结合,光谱数据表明它们是强电子给体。它们还可以经历涉及N2基团的反应,如环加成反应所证明的。

附:英文原文

Title: Isolation and characterization of diazoolefins

Author: Varava, Paul, Dong, Zhaowen, Scopelliti, Rosario, Fadaei-Tirani, Farzaneh, Severin, Kay

Issue&Volume: 2021-10-07

Abstract: Diazoolefins tend to be highly reactive compounds that rapidly lose dinitrogen. So far, most experimental evidence for diazoolefins is indirect, via trapping experiments. Here we show that diazoolefins are observed to form in reactions of N-heterocyclic olefins with nitrous oxide. The products benefit from resonance stabilization, which enables isolation on a preparative scale, and comprehensive characterization, which includes crystallographic analyses. N-heterocyclic diazoolefins show a strong ylidic character, with a high charge density at the carbon atom next to the diazo group. Despite the presence of terminal N2 groups, N-heterocyclic diazoolefins display a good thermal stability, which surpasses that observed for most diazoalkanes. N-heterocyclic diazoolefins can bind transition and main group metal complexes without the liberation of dinitrogen, and spectroscopic data show that they are strong electron donors. They can also undergo reactions that involve the N2 group, as evidenced by cycloaddition reactions.

DOI: 10.1038/s41557-021-00790-3

Source: https://www.nature.com/articles/s41557-021-00790-3

期刊信息

Nature Chemistry:《自然—化学》,创刊于2009年。隶属于施普林格·自然出版集团,最新IF:21.687
官方网址:https://www.nature.com/nchem/
投稿链接:https://mts-nchem.nature.com/cgi-bin/main.plex