Ringexpansion of N-Heterocyclic Carbenes

N-杂环卡宾的扩环

• 批准号: 316481056
• 负责人: Professor Dr. Udo Radius
• 金额: --
• 依托单位: Institut für Anorganische Chemie
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2016
• 资助国家: 德国
• 起止时间: 2015-12-31 至 2023-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/316481056?language=en
• 关键词: Ringexpansion; Heterocyclic; Carbenes

Our recent work demonstrates that N-heterocyclic carbenes (NHCs) are by far less stable than generally expected. These molecules undergo ring expansion reactions (RER) with destruction of the NHC core structure especially when they were reacted with main group element (MGE) hydrides. Furthermore, we have shown for the reaction of selected MGE hydrides with NHCs that dehydrogenative element element coupling occurs; the NHC serves in these cases as a hydrogen acceptor. In our future work we want to continue with the systematic investigation of RERs of NHCs and NHC-mediated dehydrocoupling of MGE hydrides, with a focus on the heavier group 13 (Ga/In), group14 (Ge/Sn/Pb), and group 15 (P/As/Sb) elements. Furthermore, we want to explore the use of NHC adducts of group 13 hydrides of the type (NHC)·EH2X and (NHC)∙EHX2 (E = Al, Ga, In), respectively, as synthetic equivalents for subvalent entities “EX” and “EX2“ and we want to answer the question whether our results on the ring exansion of NHCs can be transferred to a possible RER of N-heterocyclic Silylenes in the reaction with MGE halides. Moreover, we want to try to convert the RER products into novel 6-ring carbenes or silylenes.

我们最近的工作表明，N-杂环卡宾（NHC）的稳定性远远低于一般预期。这些分子经历扩环反应（RER），破坏NHC核心结构，特别是当它们与主族元素（MGE）反应时。此外，我们已经表明，对于所选的MGE与NHC的反应，会发生双价元素偶联;在这些情况下，NHC充当氢受体。在我们未来的工作中，我们希望继续系统地研究NHC的RERs和NHC介导的MGE的脱氢偶联，重点是重13族（Ga/In），14族（Ge/Sn/Pb）和15族（P/As/Sb）元素。此外，我们想探索使用的NHC加合物的第13族的类型（NHC）·EH 2X和（NHC）EHX 2（E = Al，Ga，In），分别作为合成等价物的subvalent实体“EX”和“EX 2”，我们想回答的问题，我们的结果在环扩展的NHC是否可以转移到一个可能的RER的N-杂环甲硅烷基与MGE卤化物的反应。此外，我们想尝试将RER产物转化为新的6-环卡宾或亚甲硅烷基。