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Pseudohalogen Chemistry in Ionic Liquids with Non-innocent Cations and Anions
2020, Arlt, Sören, Bläsing, Kevin, Harloff, Jörg, Laatz, Karoline Charlotte, Michalik, Dirk, Nier, Simon, Schulz, Axel, Stoer, Philip, Stoffers, Alrik, Villinger, Alexander
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]2[B(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]2[Si(CN)6] with MOH (M=Li, K), Li2[Si(CN)6] ⋅ 2 H2O and K2[Si(CN)6] were obtained, which form three dimensional coordination polymers. From salt metathesis processes of M2[Si(CN)6] with different imidazolium bromides, we were able to isolate new imidazolium salts and the ionic liquid [BMIm]2[Si(CN)6]. When reacting [Mes(nBu)Im]2[Si(CN)6] with an excess of the strong Lewis acid B(C6F5)3, the voluminous adduct anion {Si[CN⋅B(C6F5)3]6}2− was obtained. © 2020 The Authors. Published by Wiley-VCH GmbH
Hexacyanidosilicates with Functionalized Imidazolium Counterions
2020, Harloff, Jörg, Laatz, Karoline Charlotte, Lerch, Swantje, Schulz, Axel, Stoer, Philip, Strassner, Thomas, Villinger, Alexander
Functionalized imidazolium cations were combined with the hexacyanidosilicate anion, [Si(CN)6]2–, by salt metathesis reactions with K2[Si(CN)6], yielding novel ionic compounds of the general formula [R–Ph(nBu)Im]2[Si(CN)6] {R = 2-Me (1), 4-Me (2), 2,4,6-Me = Mes (3), 2-MeO (4), 2,4-F (5), 4-Br (6); Im = imidazolium}. All synthesized imidazolium hexacyanidosilicates decompose upon thermal treatment above 95 °C (96 – 164 °C). Furthermore, the hexa-borane-adduct [Mes(nBu)Im]2{Si[(CN)B(C6F5)3]6}·6CH2Cl2 (7), which is thermally stable up to 215 °C, was obtained from the reaction of 3 with Lewis acidic B(C6F5)3. In CH3CN solution, decomposition of the hexaadduct to the Lewis-acid-base adduct CH3CN–B(C6F5)3 and [(C6F5)3B·(µ-CN)·B(C6F5)3]– was observed. All synthesized compounds were isolated in good yields and were completely characterized including single crystal structure elucidations. © 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.