Cyanidosilicates – Synthesis and Structure

Starting from fluoridosilicate precursors in neat cyano‐trimethylsilane, Me3Si‐CN, a series of different ammonium salts [R3NMe]+ (R = Et, nPr, nBu) with the novel [SiF(CN)5]2− and [Si(CN)6]2− dianions were synthesized in facile, temperature controlled F− / CN− exchange reactions. Utilizing decomposable, non‐innocent cations such as [R3NH]+, it was possible to generate metal salts of the type M2[Si(CN)6] (M+ = Li+, K+) via neutralization reactions with the corres¬ponding metal hydroxides. The ionic liquid [BMIm]2[Si(CN)6] (m. p. = 72 °C, BMIm = 1‐butyl‐3‐methylimidazolium) was obtained by salt metathesis reaction. All synthesized salts could be isolated in good yields and were fully characterized.

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