Thermochemical characteristics of solvation of ions in mixtures of water with formamide, dimethylsulfoxide and hexamethylphosphoric triamide

Enthalpies and Entropies of Transfer of Electrolytes and Ions from Water to Mixed Aqueous Organic Solvents

“…For KCl (and at one solvent concentration, KI) data from the Łodz group 298,299 are in excellent agreement with those of Vorob'ev et al The key salt, NaBPh 4 , has been extensively studied by two groups 268,297,299 across the whole range of solvent composition. The relationship between the two data sets reported by Vandyshev et al , is unclear; the reported data differ, but it is not obvious whether the later data involve new measurements or a recalculation of the earlier results. Nevertheless, the differences are generally small (apart from the data at x HMPT ≤ 0.2) and the values are in good agreement with those of Taniewska-Osinska and Jozwiak, enabling the averaged values to be Recommended.…”

“… a Data also available at 278.15 and 288.15 K. b Authors in ref are the same as ref , but the data were presented at fewer x FA , so interpolations values led to somewhat different values of Δ t H °. …”

“…A comprehensive set of enthalpies of transfer for Ph 4 PBr, NaBPh 4 , and KBr , permit estimation of Δ t H °(ion, w → w + FA) via the TPTB assumption (Table ). As the whole-salt data for this system are mostly unconfirmed, little can be said about the reliability of the single-ion values.…”

Computational Studies on the Reaction from Silyl 1,4‐Dilithio 1,3‐butadiene to Lithio Silole

“…Experimentally, the lithio silole was produced in the presence of HMPA. HMPA enhances the rates for a variety of organolithium reactions because the Li + cation is strongly solvated by HMPA . This suggests that HMPA plays an important role beyond the simple solvation of the Li + cation, particularly in the reactions of 1 .…”

“…HMPA enhances the rates for a variety of organolithium reactions 46 because the Li + cation is strongly solvated by HMPA. [48][49][50][51][52][53] This suggests that HMPA plays an important role beyond the simple solvation of the Li + cation, particularly in the reactions of 1. If the Li atoms (as Li + cations) in 1 are strongly solvated by HMPA, the bonding interactions between Li atoms and two terminal carbon atoms could be weakened and the remaining fragment of 1 will exhibit anionic character.…”