Stability of crown-ether complexes with alkali-metal ions in ionic liquid-water mixed solvents

Abstract

Stability constants of sodium and cesium ion complexes with 18-crown-6 (18C6) and dibenzo-18-crown-6 (DB18C6) in N-butyl-4-methyl-pyridinium tetrafluoroborate [BMP][BF4] aqueous solutions were measured using the 23Na and 133Cs NMR technique at 23 °C. To the best of our knowledge, the estimated values of stability constants reported in this study are the first such values given for ionic liquid solutions. The cationic exchange between the free and complexed species is rapid, and only formation of the 1:1 complexes [M(18C6)]+ and [M(DB18C6)]+ (M = Na+, Cs+) were observed. The complex formation constants demonstrated a strong dependence on the [BMP][BF4] concentration. For [M(18C6)]+, in solutions with a 0.33–0.70 mole fraction of water in [BMP][BF4], lg K values are found to be more than one unit higher than the lg K values measured in pure aqueous solutions, although no information concerning the influence of [BMP][BF4] on the complex formation selectivity could be observed. DB18C6 complexes revealed significantly lower stability under the same conditions. An extrapolation to zero water content gave the lg K = 2.42 for [Cs(18C6)]+ in [BMP][BF4]. It was discovered that when added to water, [BMP][BF4] increases the solubility of crown ethers and decreases the solubility of alkali metal nitrates. Complex formation with crown ethers enhances the solubility of alkali metal salts in [BMP][BF4].