Two nitrile‐functionalized alkyltriflouroborate anion based complexes [(Ph3P)2N][CH3CH(BF3)CH2CN] and [K(18‐crown‐6)][CH3CH(BF3)CH2CN] were synthesized and characterized by spectroscopic methods and single X‐ray diffraction analysis. In the former complex no direct cation‐anion (F→N or F→P) interactions are observed although F···H–C hydrogen bonds are present. In the later complex all three fluorine atoms interact with the potassium cation and C–H···F hydrogen bonds are also present. The ESI‐MS spectra in methanol solution of the potassium complex show similar anion‐cation aggregation to that observed for ionic liquids, and comparisons between the two complexes and ionic liquid systems are made. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
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