Pseudohalogen Chemistry in Ionic Liquids with Non-innocent Cations and Anions

具有非无害阳离子和阴离子的离子液体中的赝卤素化学

• 批准号: 252590704
• 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: Priority Programmes
• 财政年份: 2014
• 资助国家: 德国
• 起止时间: 2013-12-31 至 2020-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/252590704?language=en
• 关键词: Pseudohalogen; Chemistry; Ionic; Liquids; Non

This project describes the utilization of Ionic Liquids (ILs) with non-innocent anions and cations to synthesize new pseudohalogen borates, silicates and phosphates. As non-innocent anions are used either decomposable ions such as carbonates ([CO2(OMe)]-), borates ([B(OMe)3A]-, [B(OMe)4]-; with A = pseudohalogen, e.g. CN, SCN, N3), silicates ([Si(OMe)4A]-) and phosphates ([OP(OMe)3A]-) or the highly nucleophilic (pseudo)halides, which also form ILs with corresponding organic cations. The goal of this project is the syntheses of new (often highly labile) pseudohalogen species such as [CO2A]-, [A...H...A]-, [B(OMe)3A]-, [B(OMe)2E1A]- (E1 = halogen), [B(OMe)E2A]- (E2 = chalkogen), [A-B-E3]- (E3 = pnictogen) and salt bearing the [SiF6-n(CN)n]2- and [PF6-n(CN)n]- ions utilizing functionalized ILs for quenching or stabilizing, respectively. Non-innocent means that the used IL is both the reaction media as well as reactant. The project splits into five interacting parts: (i) Syntheses of pure pseudohalide containing ILs from ILs with decomposable anions. Preparation of pure pseudohalide containing ILs, [Cat]+A- (A = e.g. CN, SCN, N3), is well-established. Besides, the synthesis of pseudohalide containing ILs, special emphasis will be placed on the isolation of the intermediates such as [CO2A]-.(ii) Reactions of pseudohalide containing ILs with non-metal elements (e.g. P4, S8) and their oxides and sulfides. A special emphasis will be given to the solubility problem as well as the bond activation by the highly nucleophilic pseudohalides when they are part of an IL. (iii) Reactions of pseudohalide containing ILs with pure acids of pseudohalides (HA). As these ILs contain naked pseudohalides the formation of [A...H...A]- ions upon addition of the pure HA acid should be observed and the isolation attempted.(iv) Syntheses of pseudohalogen borate, silicate and phosphate species in pseudohalide containing ILs and their reaction with persilylated compounds of group 15-17.(v) Syntheses of coordination polymers utilizing cyanido(fluorido)phosphates, -arsenates and -silicates containing ILs with decomposable cations such as [nPr3NH]+.

该项目描述了利用离子液体（IL）与非无害阴离子和阳离子来合成新的拟卤硼酸盐、硅酸盐和磷酸盐。作为非无害阴离子，使用可分解离子，例如碳酸盐 ([CO2(OMe)]-)、硼酸盐 ([B(OMe)3A]-、[B(OMe)4]-；其中 A = 假卤素，例如 CN、SCN、N3)、硅酸盐 ([Si(OMe)4A]-) 和磷酸盐 ([OP(OMe)3A]-) 或高度 亲核（拟）卤化物，也与相应的有机阳离子形成离子液体。该项目的目标是合成新的（通常高度不稳定）拟卤素物质，例如 [CO2A]-、[A...H...A]-、[B(OMe)3A]-、[B(OMe)2E1A]-（E1 = 卤素）、[B(OMe)E2A]-（E2 = 硫族元素）、[A-B-E3]-（E3 = 磷元素）和带有 [SiF6-n(CN)n]2- 和 [PF6-n(CN)n]- 离子分别利用功能化 IL 进行猝灭或稳定。非无害意味着所使用的 IL 既是反应介质又是反应物。该项目分为五个相互作用的部分：（i）从具有可分解阴离子的离子液体中合成含有纯拟卤化物的离子液体。含有 IL 的纯拟卤化物 [Cat]+A-（A = 例如 CN、SCN、N3）的制备方法已成熟。此外，含拟卤化物离子液体的合成，特别强调[CO2A]-等中间体的分离。(ii)含拟卤化物离子液体与非金属元素(如P4、S8)及其氧化物和硫化物的反应。将特别强调溶解度问题以及高亲核拟卤化物作为离子液体的一部分时的键活化问题。 (iii) 含有拟卤化物的离子液体与纯拟卤化物酸 (HA) 的反应。由于这些离子液体含有裸露的拟卤化物，因此应观察到添加纯 HA 酸后形成 [A...H...A]- 离子，并尝试进行分离。(iv) 含有拟卤化物的离子液体中拟卤硼酸盐、硅酸盐和磷酸盐的合成及其与第 15-17 族全甲硅烷基化化合物的反应。(v) 利用 含有可分解阳离子（例如 [nPr3NH]+）的离子液体的氰基（氟）磷酸盐、砷酸盐和硅酸盐。