Gleichgewicht zwischen Kontakt‐ und solvensseparierten Ionenpaaren in Mischungen von protischen ionischen Flüssigkeiten und molekularen Lösungsmitteln durch Polarität kontrolliert

Fumino, Koichi; Stange, Peter; Fossog, Verlaine; Hempelmann, Rolf; Ludwig, Ralf

doi:10.1002/ange.201303944

Cited by 11 publications

(3 citation statements)

References 42 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Additionally we now detect a new vibrational band at 150 cm −1 . In recent work we could assign this vibrational band to the + NH⋅⋅⋅OS(CH 3 ) 2 interaction between the cation and solvent molecule in [Et 3 NH][CF 3 SO 3 ]/DMSO mixtures 21. The polarity of [D 6 ]DMSO is clearly required to overcome the strong cation–anion interaction and to transfer CIPs to SIPs on increasing the solvent concentration.…”

Section: Resultsmentioning

confidence: 90%

“…In recent studies for mixtures of [Et 3 NH][CH 3 SO 3 ] and water we could show that the back‐formation of CIPs is probably due to entropic reasons. In the related SIP configurations, the water molecules were tightly bound between cation and anion due to strong cooperative effects 21. The significantly reduced motional degrees of freedom resulted in an entropic penalty as indicated by the calculated Gibbs free energies for both ion‐pair configurations.…”

Section: Resultsmentioning

confidence: 99%

“…This holds in particular for PILs that include the triethylammonium ion [Et 3 NH] + as the cation. Beside the Coulomb interaction, a strong and directional hydrogen bond between the NH group of the cation and a polar atom of the anion provides strongly bound CIPs in the pure Coulomb fluid 19–21. Although each ion is surrounded by counterions, the tight cation–anion interaction leads to the existence of quasi CIPs in the neat PIL.…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Ion Pairing in Protic Ionic Liquids Probed by Far‐Infrared Spectroscopy: Effects of Solvent Polarity and Temperature

et al. 2014

Self Cite

View full text Add to dashboard Cite

The cation-anion and cation-solvent interactions in solutions of the protic ionic liquid (PIL) [Et3NH][I] dissolved in solvents of different polarities are studied by means of far infrared vibrational (FIR) spectroscopy and density functional theory (DFT) calculations. The dissociation of contact ion pairs (CIPs) and the resulting formation of solvent-separated ion pairs (SIPs) can be observed and analyzed as a function of solvent concentration, solvent polarity, and temperature. In apolar environments, the CIPs dominate for all solvent concentrations and temperatures. At high concentrations of polar solvents, SIPs are favored over CIPs. For these PIL/solvent mixtures, CIPs are reformed by increasing the temperature due to the reduced polarity of the solvent. Overall, this approach provides equilibrium constants, free energies, enthalpies, and entropies for ion-pair formation in trialkylammonium-containing PILs. These results have important implications for the understanding of solvation chemistry and the reactivity of ionic liquids.

show abstract

Section: Resultsmentioning

confidence: 90%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Ion Pairing in Protic Ionic Liquids Probed by Far‐Infrared Spectroscopy: Effects of Solvent Polarity and Temperature

et al. 2014

Self Cite

View full text Add to dashboard Cite

show abstract

The Formation of Imidazolium Salt Intimate (Contact) Ion Pairs in Solution

et al. 2014

View full text Add to dashboard Cite

1-n-Butyl-2,3-dimethylimidazolium (BMMI) ionic liquids (ILs) associated with different anions undergo H/D exchange preferentially at 2-Me group of the imidazolium in deuterated solvents. This process is mainly related to the existence of ion pairs rather than the anion basicity. The H/D exchange occurs in solvents (CDCl 3 and MeCN for instance) in which intimate contact ion pairs are present and the anion possesses a labile H in its structure, such as hydrogen carbonate and prolinate. In D 2 O, separated ion pairs are formed and the H/D exchange does not occur. A plausible catalytic cycle is that the IL behaves as a neutral base in the course of all H/D exchange processes. NMR experiments, density functional calculations, and molecular dynamics simulations corroborate these hypotheses.

show abstract

The Formation of Imidazolium Salt Intimate (Contact) Ion Pairs in Solution

Zanatta¹,

Girard²,

Simon³

et al. 2014

Angew Chem Int Ed

View full text Add to dashboard Cite

1-n-Butyl-2,3-dimethylimidazolium (BMMI) ionic liquids (ILs) associated with different anions undergo H/D exchange preferentially at 2-Me group of the imidazolium in deuterated solvents. This process is mainly related to the existence of ion pairs rather than the anion basicity. The H/D exchange occurs in solvents (CDCl3 and MeCN for instance) in which intimate contact ion pairs are present and the anion possesses a labile H in its structure, such as hydrogen carbonate and prolinate. In D2 O, separated ion pairs are formed and the H/D exchange does not occur. A plausible catalytic cycle is that the IL behaves as a neutral base in the course of all H/D exchange processes. NMR experiments, density functional calculations, and molecular dynamics simulations corroborate these hypotheses.

show abstract

Gleichgewicht zwischen Kontakt‐ und solvensseparierten Ionenpaaren in Mischungen von protischen ionischen Flüssigkeiten und molekularen Lösungsmitteln durch Polarität kontrolliert

Cited by 11 publications

References 42 publications

Ion Pairing in Protic Ionic Liquids Probed by Far‐Infrared Spectroscopy: Effects of Solvent Polarity and Temperature

Ion Pairing in Protic Ionic Liquids Probed by Far‐Infrared Spectroscopy: Effects of Solvent Polarity and Temperature

The Formation of Imidazolium Salt Intimate (Contact) Ion Pairs in Solution

The Formation of Imidazolium Salt Intimate (Contact) Ion Pairs in Solution

Contact Info

Product

Resources

About