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]+.

该项目描述了具有非纯净阴离子和阳离子的离子液体（IL）的利用，以合成新的pseudohalalogen硼酸盐，硅酸盐和磷酸盐。 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亲核（伪）卤化物，它也形成与相应有机阳离子的IL。该项目的目标是新（通常非常不稳定的）假alalogen物质的合成，例如[CO2A] - ，[A ... H ... H ... A] - ，[B（OME）3A] - ，[B（OME）2E1A] - （e1 = halogen） - （E1 =卤素） [SIF6-N（CN）N] 2和[PF6-N（CN）N] - 利用功能化IL进行淬火或稳定的离子。非一种中心意味着使用的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）包含来自具有可分解阴离子的IL的IL的纯假甲甲甲化物的合成。制备含有IL的纯假甲酯，[cat]+a-（a = e.g。cn，scn，n3）是完善的。此外，将含有IL的假甲甲化物的合成，将特别重点放在中间体的分离上，例如[CO2A] - 。（ii）含有非金属元素（例如P4，S8）及其氧化物和氧化物和氧化物和硫化物的IL的反应。当它们是IL的一部分时，将特别强调溶解度问题以及高度亲核假甲烷的键激活。 （iii）含有IL的假甲甲甲甲基甲酯的反应（HA）。由于这些IL含有裸体假甲化物，因此应观察到[A ... H ... A] - 离子的形成，并尝试观察到纯HAID，并尝试进行隔离。（iv）假钙醇，硅酸盐，硅酸盐，硅酸盐和磷酸物种的合成，含有ILS的假硫酸盐及其与持久的Poliments Poliments及其与甲壳化的合成15-17合成（V）的合成（V）。 Cyanido（氟））磷酸盐， - 动态和含有可分解阳离子的IL（例如[NPR3NH]+）的磷酸盐。