Stabilization of classical (anhydrous) Brønsted acids by the Lewis acids B(C6F5)3 and [Me3Si]+

路易斯酸 B(C6F5)3 和 [Me3Si] 稳定经典（无水）布朗斯台德酸

• 批准号: 321319519
• 负责人: Professor Dr. Axel Schulz
• 金额: --
• 依托单位: Lehrstuhl für Anorganische und Elementorganische 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/321319519?language=en
• 关键词: Stabilization; classical; anhydrous; Br; nsted

The aim of the research project is the synthesis and adduct stabilization of simple (mostly labile) planar, resonance-stabilized pseudohalogen acids (H-X, X = C(CN)3-, H(CN)NO-, H(CN)NO2-, HC(NO)2-, C(NO2)3-, NC-N-CN-, NC-N-NO2-, etc.) as well as their silylated homologues (Me3Si-X), which have not yet been investigated in the first period. Adduct stabilization is to be carried out on the one hand by the bulky, neutral Lewis acid B(C6F5)3 and on the other hand by the very strong cationic Lewis acid [Me3Si]+, so that in the first case neutral acid adducts are formed (H-X-B(C6F5)3 or Me3Si-X-B(C6F5)3), while adduct formation with silylium ions leads to cations of the type [H-X-SiMe3]+ or [Me3Si-X-SiMe3]+. This approach allows the systematic investigation of the stability, structure, and bonding depending on the steric hindrance (H vs. Me3Si or B(C6F5)3 vs. [Me3Si]+) as well as the charge of the adduct system (neutral vs. cationic). Furthermore, we would like to use the anions activated by the strong electron pull in synthetic chemistry, e.g., in electrophilic aromatic substitutions. In summary, we would like to show that adduct formation can be used to stabilize especially the very labile planar resonance-stabilized pseudohaloacids and thus make them accessible in substance for subsequent reactions.

本研究项目的目的是合成简单（大多是不稳定的）平面共振稳定的拟卤酸（H-X，X = C（CN）3-，H（CN）NO-，H（CN）NO2-，HC（NO）2-，C（NO2）3-，NC-N-CN-，NC-N-NO2-等）并使其加合物稳定。以及它们的甲硅烷基化同系物（Me 3Si-X），这在第一阶段尚未研究。加合物稳定化一方面通过大体积的中性刘易斯酸B（C6 F5）3进行，另一方面通过非常强的阳离子刘易斯酸[Me 3 Si]+进行，从而在第一种情况下形成中性酸加合物（H-X-B（C6 F5）3或Me 3 Si-X-B（C6 F5）3），而与甲硅烷基离子形成加合物会产生[H-X-SiMe 3]+或[Me 3 Si-X-SiMe 3]+类型的阳离子。该方法允许系统地研究取决于空间位阻（H vs. Me 3Si或B（C6 F5）3 vs. [Me 3Si]+）以及加合物系统的电荷（中性vs.阳离子）的稳定性、结构和键合。此外，我们希望在合成化学中使用由强电子拉力激活的阴离子，例如，亲电芳香取代反应中。总之，我们想表明，加合物的形成可用于稳定，特别是非常不稳定的平面共振稳定的拟卤酸，从而使它们在物质上可用于随后的反应。