No abstract

The solubility of H(2)S in a series of 1-butyl-3-methylimidazolium ([bmim](+)) based ionic liquids (ILs) with different anions, chloride, tetrafluoroborate ([BF(4)](-)), hexafluorophosphate ([PF(6)](-)), triflate ([TfO](-)), and bis(trifluoromethyl)sulfonylimide ([Tf(2)N]-), and in a series of [Tf(2)N] ILs with different cations, i.e., N-alkyl-N'-methylimidazolium, 2-methyl-N-methyl-N'-alkyimidazolium, N-alkylpyridinium, N-butyl-N-methylpyrrolidinium, and N-alkyl-N,N-dimethyl-N-(2-hydroxyethyl)ammonium has been determined using medium-pressure NMR spectroscopy. The observed solubilities are significantly higher than those reported for many other gases in ILs, suggesting the occurrence of specific interactions between H2S and the examined ILs. Quantum chemical calculations have been used to investigate at a molecular level the interaction between H2S and the [bmim](+)-based ILs.

The polarity of a series of ionic liquids (ILs) arising from the quaternarization of N-methylmorpholine, N-methylpyrrolidine, N-methylpiperidine, N-methylazepane, 4-hydroxy-1-methylpiperidine, 1,2-dimethylimidazole, and 1-methylimidazole with simple alkyl chains and/or hydroxyl (mono- or dihydroxyl) functionalized alkyl chains and having bistriflimide, dicyanamide, or nitrate as counteranions has been investigated using solvatochromic dyes and expressed in terms of E(T)(N) and Kamlet-Taft parameters (dipolarity/polarizability (π*), hydrogen bond donor acidity (α), and hydrogen bond basicity (β)). Significant variations of polarity were observed on changing the anion and cation combination. The resulting E(T)(N) and α values were strongly anion dependent; on going from bistriflimide to dicyanamide, a significant decrease in E(T)(N) and α values was observed. On the other hand, the alkyl chain length has only a moderate effect on these parameters; either an increase or decrease in E(T)(N) and α values was observed on increasing the alkyl chain length, depending on the cation core. In the case of cyclic onium salts, the size of the cation ring affected the α parameter; the ILs based on the seven-membered ring system N-methyl-N-butylazepanium (also named N-methyl-N-butylhexamethyleneiminium, [HME(1,4)](+)) have high polarity values, comparatively to the ILs based on analogous five- and six-membered cyclic cations (pyrrolidinium and piperidinium). The introduction of the OH groups on the cation alkyl chain increases the polarity; the effect is substantial for the first OH group and more moderate for the second. Also, the thermosolvatochromism (changes in solvatochromic properties with the change in temperature) was studied for four dihydroxyl functionalized ILs. Finally, the principal component analysis (PCA) carried out on 67 ILs has shown that there are only two statistically relevant parameters: PC1, a weighted sum of E(T)(N) and α, which is able to discern between the cation core structure, functionalization, and cation-anion association, and PC2, very close to β, which is related principally to the anion nature.

The Diels-Alder reaction between cyclopentadiene and three dienophiles (acrolein, methyl acrylate and acrylonitrile) having different hydrogen bond acceptor abilities has been carried out in several ionic liquids and molecular solvents in order to obtain information about the factors affecting reactivity and selectivity. The solvent effects on these reactions are examined using multiparameter linear solvation energy relationships. The collected data provide evidence that the solvent effects are a function of both the solvent and the solute. For a solvent effect to be seen, the solute must have a complimentary character; selectivities and rates are determined by the solvent hydrogen bond donation ability (alpha) in the reactions of acrolein and methyl acrylate, but not of acrylonitrile.