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

本项目介绍了利用非无害阴离子和阳离子离子液体合成新型假卤素硼酸盐、硅酸盐和磷酸盐。由于非无害阴离子被用于可分解离子，如碳酸盐（[CO2(OMe)]-），硼酸盐([B(OMe)3A]-, [B(OMe)4]-；与A =假卤素，如CN， SCN, N3)，硅酸盐（[Si(OMe)4A]-）和磷酸盐（[OP(OMe)3A]-）或高度亲核的（伪）卤化物，它们也与相应的有机阳离子形成ILs。该项目的目标是合成新的（通常是高度不稳定的）假卤素物种，如[CO2A]-， [A…H…][A]-, [B(OMe)3A]-, [B(OMe)2E1A]- （E1 =卤素），[B(OMe)E2A]- （E2 =白垩原），[A-B-E3]- (E3 = pnicogen)和盐分别采用功能化ILs进行淬火或稳定。非无害化是指所使用的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)用可分解阴离子的白介素合成含白介素的纯假卤化物。制备了含il的纯假卤化物[Cat]+A- （A =例如CN， SCN, N3）。此外，在含il的假卤化物的合成中，将特别强调[CO2A]-等中间体的分离。（ii）含ILs的假卤化物与非金属元素（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，以及高度亲核的假卤化物在成为假卤化物的一部分时对键的激活。（iii）含假卤化物与纯假卤化物酸（HA）的反应。由于这些il含有裸假卤化物，形成[A…H…]在加入纯HA酸后，应观察A]-离子，并尝试分离。（iv）假卤素硼酸盐、硅酸盐和磷酸盐的合成及其与15-17基团的烷基化化合物的反应。（五）利用含有可分解阳离子（如[nPr3NH]+）的氰基（氟基）磷酸盐、-砷酸盐和-硅酸盐合成配位聚合物。

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]+.