Synthesis and physical properties of tris(dialkylamino)cyclopropenium dicyanamide ionic liquids

Abstract

The synthesis and properties of 16 tris(dialkylamino)cyclopropenium (TDAC) cations with the dicyanamide (DCA) anion, [N(CN)₂]⁻, are described. D_3h- and C_3h-symmetric cations ([C₃(NR₂)₃]DCA (R = Me, Et, Pr, Bu, Pent, Hex, Dec) and [C₃(NRMe)₃]DCA (R = Bu, St), respectively) were synthesised by reaction of C₃Cl₅H with the corresponding amine. Reaction of the alkoxydiaminocyclopropenium salt [C₃(NEt₂)₂(OMe)]⁺ with amines led to a series of C_2v-symmetric salts [C₃(NEt₂)₂(NR₂)]DCA (R = Me, Bu, Hex) and two C_s-symmetric salts and [C₃(NEt₂)₂(NRMe)]DCA (R = Me, Bu). Similarly, [C₃(NMe₂)₂(OMe)]⁺, was used to prepare the C_s-symmetric salts [C₃(NMe₂)₂(NRMe)]DCA (R = Pr, Bu). In addition to characterisation by NMR, mass spectrometry and microanalysis, the salts were characterised by DSC, TGA, density, viscosity, conductivity and miscibility/solubility studies. Comparisons have been made with similar series of bistriflimide (NTf₂⁻) salts that have been previously reported to see whether the same trends are observed with a different anion.