Brønsted Acid—Base Behavior in “Inert” Organic Solvents

Proton transfer reactions in apolar aprotic solvents

“…The main parameters characterizing proton transfer rate equilibria include log K (equilibrium/association constant in toluene/chlorobenzene), log k α (catalytic constant for the monomer acid in toluene/chlorobenzene), log k cat (composite catalytic constant in toluene), and log k +1 (forward rate constant in toluene), each of which can be used to frame acidity scales in an apolar aprotic solvent. Among these, those used by earlier researchers, for example, log K BHA (benzene) by Davis et al . and log k (chlorobenzene) by Chapman et al ., log k +1 (toluene) derived from pseudo‐first‐order reaction kinetics for mono‐substituted benzoic acids, and log K (chlorobenzene) derived from the equilibria for di‐substituted benzoic acids, are the most structure sensitive and rank as the most appropriate for defining acidity scales for the respective class of benzoic acids in inert solvents.…”

“…The vast majority of pre‐1980 progress since the 1920s Brønsted–Lowry proton cult in studies on the thermodynamic aspects of proton transfer between various carboxylic acids, phenols and fluoro‐alcohols/nitro‐alcohols, and organic bases of different classes in different apolar aprotic solvents by Brønsted, Hall, La Mer and Downes, Griffith, Hantzsch, Weissberger and Fasold, Barrow et al ., Cook, Gramstad, Zeegers‐Huyskens, Denisov et al ., Bruckenstein et al ., De Tar et al ., Bell et al ., Anderson, Pearson et al ., Bayles et al ., Popovych, Davis et al ., Jasinski et al ., Steigman et al ., Vinogradov et al ., Parbhoo et al ., Walker et al ., Sobczyk et al ., and Simmons et al . and their kinetic and catalytic aspects by Brønsted et al ., Hartman et al ., Bell et al ., Crooks et al ., Simmons et al ., Robinson et al ., Caldin et al ., Ivin et al ., Burfoot et al ., Palit et al ., and Chapman using infrared (IR), ultraviolet (UV)–visible spectrophotometry of the ion‐pair product and microwave and laser pulse temperature jump as well as stopped flow concentration‐jump techniques has been reviewed by Hall, La Mer and Downes, Davis, Crooks and Robinson, Robinson, Simmons, and Zeegers‐Huyskens and Huyskens…”

Ionic Pairing and Selective Solvation of Butylmethylimidazolium Chloride Ion Pair in DMSO-Water Mixtures: A Comprehensive Examination via Molecular Dynamics Simulations and Potentials of Mean Force Analysis

“…68 Extensive molecular dynamics simulations have unearthed intriguing insights, with alcohol clusters in mixtures with ILs of differing hydrophobicity degrees manifesting distinct characteristics. 69 Notably, the structural and dynamic attributes of water-alkyl-3-methylimidazolium ionic liquid mixtures exhibit dependence on both anion hydrophobicity and cation chain length. 70 Moreover, the competitive solvation behavior of the 1,3-dimethylimidazolium cation by water and methanol, despite their chemical similarities, has been unveiled, offering tantalizing prospects for future ternary ion-molecular systems.…”