Pseudohalogen Chemistry in Ionic Liquids with Non-innocent Cations and Anions |
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| Authors: | Dr Sören Arlt Dr Kevin Bläsing Dr Jörg Harloff Karoline Charlotte Laatz Dr Dirk Michalik Simon Nier Prof Axel Schulz Philip Stoer Dr Alrik Stoffers Dr Alexander Villinger |
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| Institution: | 1. Anorganische Chemie, Institut fur Chemie, Universität Rostock, A.-Einstein-Str. 3a, 18059 Rostock, Germany;2. Anorganische Chemie, Institut für Chemie, Philipps-Universität Marburg, Hans-Meerwein-Straße 4, 35032 Marburg, Germany |
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| Abstract: | Within the second funding period of the SPP 1708 “Material Synthesis near Room Temperature”,which started in 2017, we were able to synthesize novel anionic species utilizing Ionic Liquids (ILs) both, as reaction media and reactant. ILs, bearing the decomposable and non-innocent methyl carbonate anion CO3Me]?, served as starting material and enabled facile access to pseudohalide salts by reaction with Me3Si?X (X=CN, N3, OCN, SCN). Starting with the synthesized Room temperature Ionic Liquid (RT-IL) nBu3MeN]B(OMe)3(CN)], we were able to crystallize the double salt nBu3MeN]2B(OMe)3(CN)](CN). Furthermore, we studied the reaction of WCC]SCN and WCC]CN (WCC=weakly coordinating cation) with their corresponding protic acids HX (X=SCN, CN), which resulted in formation of H(NCS)2]? and the temperature labile solvate anions CN(HCN)n]? (n=2, 3). In addition, the highly labile anionic HCN solvates were obtained from PPN]X (PPN]=μ-nitridobis(triphenylphosphonium), X=N3, OCN, SCN and OCP) and HCN. Crystals of PPN]X(HCN)3] (X=N3, OCN) and PPN]SCN(HCN)2] were obtained when the crystallization was carried out at low temperatures. Interestingly, reaction of PPN]OCP with HCN was noticed, which led to the formation of P(CN)2]?, crystallizing as HCN disolvate PPN]P(CN?HCN)2]. Furthermore, we were able to isolate the novel cyanido(halido) silicate dianions of the type SiCl0.78(CN)5.22]2? and SiF(CN)5]2? and the hexa-substituted Si(CN)6]2? by temperature controlled halide/cyanide exchange reactions. By facile neutralization reactions with the non-innocent cation of Et3HN]2Si(CN)6] with MOH (M=Li, K), Li2Si(CN)6] ? 2 H2O and K2Si(CN)6] were obtained, which form three dimensional coordination polymers. From salt metathesis processes of M2Si(CN)6] with different imidazolium bromides, we were able to isolate new imidazolium salts and the ionic liquid BMIm]2Si(CN)6]. When reacting Mes(nBu)Im]2Si(CN)6] with an excess of the strong Lewis acid B(C6F5)3, the voluminous adduct anion {SiCN?B(C6F5)3]6}2? was obtained. |
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| Keywords: | pseudohalides hydrogen bonding ionic liquids silicates borates |
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