On the knowledge of the Lewis amphoteric tris(pentafluoroethyl)silanolate ion and its derivatives [Si(C2F5)3E]- (E = O, NR and CR2)

关于路易斯两性三(五氟乙基)硅烷醇根离子及其衍生物[Si(C2F5)3E]- (E = O、NR和CR2)的认识

• 批准号: 440653279
• 负责人: Professor Dr. Berthold Hoge
• 金额: --
• 依托单位: Arbeitsgruppe Anorganische Chemie II
• 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/440653279?language=en
• 关键词: knowledge; Lewis; amphoteric; tris; pentafluoroethyl

Utilizing the strong electron-withdrawing effect of the pentafluoroethyl group, we are able to realize a LEWIS amphoteric character in the tris(pentafluoroethyl)silanide ion, [Si(C2F5)3]¬–, on the one hand, and to stabilize negative charges in alpha-position to the Si(C2F5)3 unit, such as in [(C2F5)3Si-CR2]– or [(C2F5)3Si-NR]– derivatives, on the other hand. We would like to study the LEWIS amphoteric behavior of the [Si(C2F5)3]– ion based on its reactions with polar multiple as well as single bonds. In this context, we expect further unusual reactions as observed for example in the oxidative addition of Ph2PCl. This reaction subsequently leads to a reductive coupling with another equivalent of Ph2PCl yielding in the formation of Ph2P-PPh2 and the oxidation of the silanide ion to the dichlorosilicate [Si(C2F5)3Cl2]–. The generation of carbanionic species, such as the [(C2F5)3Si-CH2]– ion, also leads to some unusual secondary products: The nucleophilic attack of [(C2F5)3Si-CH2]– on a second equivalent of the substrate, (C2F5)3Si-CH3, leads, after the elimination of C2F5H, to the anionic species [(C2F5)3Si-CH-Si(C2F5)2CH3]–, in which the negative charge on the central C atom is stabilized by two silane units. We would like to employ two tris(pentafluoroethyl)silanyl units for the stabilization of isolobal carbodiphosphorane systems and, of course, investigate in detail the reactivity of the dianionic compound [(C2F5)3Si=C=Si(C2F5)2]2–.

利用五氟乙基群的强大电子与绘图效应，我们能够在Tris（pentafluoroethyl）硅烷硅烷离子中实现刘易斯的两次化特征，[si（c2f5）3] - ，一方[（C2F5）3SI-CR2] - 或[（C2F5）3SI-NR] - 另一方面。我们想研究[si（c2f5）3] - 离子的刘易斯两性行为，基于其与极性多重和单键的反应。在这种情况下，我们期望在PH2PCL的氧化添加中观察到的进一步的异常反应。随后，该反应导致在PH2P-PPH2形成中与另一种等效的PH2PCL屈服的耦合，并将硅烷离子氧化与二氯硅酸盐[SI（C2F5）3Cl2] - 。碳物种的产生，例如[（C2F5）3SI-CH2] - 离子，也导致了一些不寻常的次要产品：[（C2F5）3SI-CH2]的核直生性攻击 - 在底物的第二次等同上[（C2F5）3SI-CH-SI（C2F5）2CH3] - 中央C原子上的负电荷被两个硅烷单元稳定。我们希望使用两个Tris（五氟乙基）硅烷基单元稳定孤立的碳纤维磷酸酯系统，当然，还详细研究了Dianionic化合物的反应性[（C2F5）3SI = C = C = SI（C2F5）2] 2-2--