Radicals in the coordination sphere of silicon

硅配位层中的自由基

• 批准号: 278990444
• 负责人: Professor Dr. Herbert Roesky, Ph.D.
• 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: 2015
• 资助国家: 德国
• 起止时间: 2014-12-31 至 2017-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/278990444?language=en
• 关键词: Radicals; coordination; sphere; silicon

The chemistry of NHC3 (NHC = N-heterocyclic carbene) has been intensively investigated. However, the chemistry of cAACs (cAAC = cyclic alkylamino carbene) is still in its infancy. The already known results of cAACs show a distinct direction for the development of practical useful species. According to the small HOMO-LUMO gap of cAAC compounds they can be used distinctively for the synthesis of molecules with radical character. This is a new route which we have established and which leads to intermediates or end products with radical character. In this research proposal dichlorosilylene-phosphinidenes and carbon-silylene radicals will be prepared and their applications studied in detail. Dichlorosilylene-phosphinidenes show an intramolecular charge transfer, which causes the different colors of the NHC and cAAC adducts. Moreover, we are aiming at preparing the first carbon-silylene radicals. The latter species will be used for the activation of small molecules such as CO2, H2, and N2, and also for the activation of C-H and N-H bonds and for selective preparations of transition metal complexes.

NHC3 （NHC = n -杂环碳）的化学性质得到了深入的研究。然而，cAAC （cAAC =环烷基胺碳）的化学研究仍处于起步阶段。已知的caac结果为实际有用物种的发展指明了明确的方向。由于cAAC化合物具有较小的HOMO-LUMO间隙，因此它们可以独特地用于合成具有自由基性质的分子。这是我们已经建立的一条新路线，它会导致中间体或具有激进特征的最终产品。本研究拟制备二氯硅膦基和碳硅基自由基，并对其应用进行详细研究。二氯硅烯-膦酸酯表现出分子内电荷转移，导致NHC和cAAC加合物的颜色不同。此外，我们的目标是制备第一个碳-硅烯自由基。后一种物质将用于小分子如CO2、H2和N2的活化，也用于C-H和N-H键的活化以及过渡金属配合物的选择性制备。