Radicals in the coordination sphere of silicon

NHC 3（NHC = N-杂环卡宾）的化学已被深入研究。然而，cAAC（cAAC =环状烷基氨基卡宾）的化学仍处于起步阶段。cAAC的已知结果显示了开发实用有用物种的独特方向。由于cAAC化合物的HOMO-LUMO能隙小，它们可被独特地用于合成具有自由基特征的分子。这是我们已经建立的一种新的路线，它导致具有自由基特征的中间体或最终产物。在本研究计划中，将制备二氯亚硅基膦和碳亚硅基自由基，并详细研究它们的应用。二氯甲硅烷基-膦酰亚胺显示分子内电荷转移，这导致NHC和cAAC加合物的不同颜色。此外，我们的目标是制备第一个碳-甲硅烷基自由基。后一种物质将用于活化小分子如CO2、H2和N2，也用于活化C-H和N-H键，以及用于选择性制备过渡金属络合物。

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.