Cyclic (alkyl)(amino)carbenes with a 1,1'-ferrocenediyl backbone

具有 1,1-二茂铁二基主链的环状（烷基）（氨基）卡宾

• 批准号: 469365488
• 负责人: Professor Dr. Ulrich Siemeling
• 金额: --
• 依托单位: Fachgebiet Metallorganische Chemie
• 依托单位国家: 德国
• 项目类别: Research Grants
• 资助国家: 德国
• 项目状态: 未结题
• 来源: https://gepris.dfg.de/gepris/projekt/469365488?language=en
• 关键词: Cyclic; alkyl; amino; carbenes; ferrocenediyl

Cyclic (alkyl)(amino)carbenes (CAACs) exhibit a significantly more pronounced ambiphilicity than classic “Arduengo type” N-heterocyclic carbenes (NHCs) and are thus able to activate fundamentally important small molecules such as, for example, CO and NH3 already under mild conditions. N-heterocyclic carbenes with a 1,1’-ferrocenediyl backbone (fcNHCs) are similar in this respect to CAACs, since their pronounced ambiphilicity, and hence high reactivity, is quite unusual for NHCs. In this project, both types of particularly ambiphilic carbenes, viz. CAACs and fcNHCs, will be combined. The project aims at gaining access to cyclic (alkyl)(amino)carbenes with a 1,1’ferrocendiyl backbone (fcCAACs) and studying them in terms of their steric and electronic properties as well as their reactivity. Differences with respect to established CAACs will be of particular interest. According to our hypothesis, fcCAACs will exhibit a particularly pronounced ambiphilicity, and hence particularly high reactivity. Consequently, we will specifically study their capability for small-molecule activation – a task where fcCAACs are expected to be superior to established CAACs. Furthermore, we surmise that the ability for stabilizing (metallo-)radicals, which is typical for CAACs, may be strengthened markedly by the presence of the redox-active 1,1’-ferrocenediyl backbone, giving access to novel stable oligoradicals.

环(烷基)(氨基)卡宾(CAAC)比经典的“Arduengo型”N-杂环卡宾(NHCs)表现出更明显的亲水性，因此能够在温和的条件下激活基本重要的小分子，如CO和NH3。具有1，1‘-二茂铁二基主链的N-杂环卡宾(FcNHC)在这方面与CAAC相似，因为它们明显的两亲性，因此具有很高的反应活性，在NHCS中是相当不寻常的。在这个项目中，这两种类型的特别亲双亲的卡宾，即。CAAC和fcNHC将合并。该项目旨在获得具有1，1‘-二茂铁二基主链的环(烷基)(氨基)卡宾(FcCAAC)，并研究它们的空间和电子性质以及它们的反应活性。关于已建立的CAAC的差异将特别令人感兴趣。根据我们的假设，fcCAAC将表现出特别明显的两亲性，因此反应活性特别高。因此，我们将专门研究它们的小分子激活能力--在这项任务中，fcCAAC有望优于现有的CAAC。此外，我们推测，氧化还原活性的1，1‘-二茂铁二基主链的存在可能会显著增强CAAC的稳定(金属)自由基的能力，从而获得新的稳定的寡聚化合物。