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.