Standard p<i>K</i>_a Scales of Carbon-Centered Indicator Acids in Ionic Liquids: Effect of Media and Structural Implication

Abstract

Energetics of bond dissociation, especially the R–H bond heterolysis free energy (p<i>K</i>_a), has played a central role in promoting chemistry to become a rational science. Despite the oceans of acidity studies in the literature, the current knowledge is limited to that in the classical molecular solvents and is unable to be extended to anticipate the acidity changes in ionic media. As the latter is now very popular for replacing volatile organic solvents, it becomes highly desirable to know how the driving force of bond cleavage is varied as the medium composition is switched from neutral <i>molecules</i> to the charged <i>ions</i>. Here we describe a general approach to measure absolute p<i>K</i>_a’s in pure ionic liquid (IL). The standard conditions warranting accurate measurement were outlined. The p<i>K</i>_a’s of the selected 18 C–H type indicator acids in four ILs were determined and a convenient indicator platform was constructed for easy expansion of acidity scales. These absolute p<i>K</i>_a’s make possible, for the first time, direct comparisons of bond energies in IL with those in molecular solvent and in the gas phase and should be able to serve as the standard parameters for calibrating computational methods suitable for the studies in ionic media. The effect of cation and anion in IL in relation to structure was analyzed