Conformational design concepts for anions in ionic liquids

Philippi, Frederik; Pugh, David; Rauber, Daniel; Welton, Tom; Hunt, Patricia A.

doi:10.1039/d0sc01379j

Cited by 41 publications

(72 citation statements)

References 101 publications

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“…Anions of different conformational flexibility were chosen for this study based upon a preceding theoretical study. 18 Ionic liquids with the 2,2,2-trifluoro-N-(trifluoromethanesulfonyl)acetamide, [NTfTFA] À , anion are known to have high fluidities and low melting points, similar to those with the [NTf 2 ] À anion. 51 Both [NTfTFA] À and [NTf 2 ] À are of comparable flexibility, however their potential energy surfaces exhibit qualitatively different minima.…”

Section: Choice Of Model Systemmentioning

confidence: 99%

“…51 Both [NTfTFA] À and [NTf 2 ] À are of comparable flexibility, however their potential energy surfaces exhibit qualitatively different minima. 18 The [CHTf 2 ] À anion is formally obtained from [NTf 2 ] À by replacing the imide group with a methanide group. Thus, the two anions have almost the same molecular weight, the same degree of fluorination, and a comparable acidity for their conjugate acids.…”

Section: Choice Of Model Systemmentioning

confidence: 99%

“…52,53 The only significant difference between [CHTf 2 ] À and [NTf 2 ] À is their conformational flexibility. 18…”

Section: Choice Of Model Systemmentioning

confidence: 99%

“…The main difference between [NTf 2 ] À and [CHTf 2 ] À is the barrier for rotation around the C-S-X-S dihedral, with X = C or N. The barrier for rotation is much higher for [CHTf 2 ] À than for [NTf 2 ] À , as will be shown shortly in the Theory section. 18 [P(2O2) 3…”

Section: Thermal Properties and Densitymentioning

confidence: 99%

“…A recurring concept relevant to almost all properties of ionic liquids is conformational flexibility. 10,18 ILs are typically composed of at least one organic ion, which usually exist in more than one conformer. If the energy barrier for interconversion between these conformers is small compared to the thermal energy available at the temperature of the liquid, then the ion has a high conformational flexibility.…”

Section: Introductionmentioning

confidence: 99%

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Ether functionalisation, ion conformation and the optimisation of macroscopic properties in ionic liquids

Philippi

Rauber

Kuttich

et al. 2020

Phys. Chem. Chem. Phys.

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Section: Choice Of Model Systemmentioning

confidence: 99%

Section: Choice Of Model Systemmentioning

confidence: 99%

“…52,53 The only significant difference between [CHTf 2 ] À and [NTf 2 ] À is their conformational flexibility. 18…”

Section: Choice Of Model Systemmentioning

confidence: 99%

Section: Thermal Properties and Densitymentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Ether functionalisation, ion conformation and the optimisation of macroscopic properties in ionic liquids

Philippi

Rauber

Kuttich

et al. 2020

Phys. Chem. Chem. Phys.

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Selenium‐NMR Spectroscopy in Organic Synthesis: From Structural Characterization Toward New Investigations

et al. 2020

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This review article deals with organic synthesis from the perspective of selenium-77 nuclear magnetic resonance (NMR) spectroscopy. Different types of organic reactions are briefly discussed, incorporating mechanism aspects through 77 Se NMR observable intermediates and byproducts. The 77 Se NMR experiments are demonstrated in terms of structural characterization and new insights for organic reactions. The ability to visualize different molecules in a reaction mixture provides a facile and versatile route for the development of synthetic organoselenium compounds. Thus, the review describes the strategies accomplished mainly in the past five years in the syntheses and applications of the organoselenium compounds, focusing on 77 Se NMR spectroscopy.

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Selective Chirality Transfer to the Bis(trifluoromethylsulfonyl)imide Anion of an Ionic Liquid

Blasius

Kirchner

2023

Chemistry A European J

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Chirality transfer from the chiral molecule (R)‐1,2‐propylene oxide to the achiral anion of the 1‐ethyl‐3‐methylimidazolium bis(trifluoromethylsulfonyl)imide ionic liquid is observed. The chiral probe selectively affects one part of the binary ionic liquid, i. e., it has previously been shown experimentally and theoretically that this particular imidazolium cation can be affected by chirality transfer, but in the present system chirality is almost exclusively transferred to the anion and not to both parts of the solvent (anion and cation). This observation is of high relevance because of its selectivity and because anion effects are usually much more important in ionic liquid research than cation effects. From ab initio molecular dynamics simulations, a conformational analysis and dissected vibrational circular dichroism spectra are obtained to study the chirality transfer. While in the neat ionic liquid two mirror imaged trans conformers of the anion occur almost equally, we observe an excess of one of these conformers in the presence of the chiral solute, causing optical activity of the anion. Although the cis conformers are not tremendously affected by the chirality transfer, they gain in total population when (R)‐1,2‐propylene oxide is dissolved in the ionic liquid.

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Conformational design concepts for anions in ionic liquids

Abstract:
Interchangeable functional groups for imide ions are investigated computationally, new ILs with low/high viscosity are designed a priori and experimentally characterised.

Cited by 41 publications

References 101 publications

Ether functionalisation, ion conformation and the optimisation of macroscopic properties in ionic liquids

Ether functionalisation, ion conformation and the optimisation of macroscopic properties in ionic liquids

Selenium‐NMR Spectroscopy in Organic Synthesis: From Structural Characterization Toward New Investigations

Selective Chirality Transfer to the Bis(trifluoromethylsulfonyl)imide Anion of an Ionic Liquid

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Conformational design concepts for anions in ionic liquids

Abstract: Interchangeable functional groups for imide ions are investigated computationally, new ILs with low/high viscosity are designed a priori and experimentally characterised.

Cited by 41 publications

References 101 publications

Ether functionalisation, ion conformation and the optimisation of macroscopic properties in ionic liquids

Ether functionalisation, ion conformation and the optimisation of macroscopic properties in ionic liquids

Selenium‐NMR Spectroscopy in Organic Synthesis: From Structural Characterization Toward New Investigations

Selective Chirality Transfer to the Bis(trifluoromethylsulfonyl)imide Anion of an Ionic Liquid

Contact Info

Product

Resources

About

Abstract:
Interchangeable functional groups for imide ions are investigated computationally, new ILs with low/high viscosity are designed a priori and experimentally characterised.