Structure of bis(trifluoromethanesulfonyl)imide in inert and protophilic media

Chípanina, N. N.; Sterkhova, Irina V.; Aksamentova, T. N.; Sherstyannikova, L. V.; Kukhareva, V. A.; Shainyan, B. А.

doi:10.1134/s1070363208120128

Cited by 15 publications

(15 citation statements)

References 26 publications

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“…1‐(1‐Ethyl‐3‐imidazolium)propane‐3‐sulfonate (EIMS, p K a ≈6.8) is a zwitterionic liquid, which has both a cation and anion that are tethered together and cannot migrate along potential gradients, and thus may favor proton conduction only . Mixing EIMS with N , N ‐bis(trifluoromethanesulfonyl)amide (HTFSA, p K a ≈2), forms a Brønsted acid–base buffer (Scheme a) . In this mixture, the protonated ‐SO 3 H/HTFSA and unprotonated ‐SO 3 − /TFSA − matrix thus act as proton‐source, and proton‐defect sites, respectively, enabling H + hopping between the negatively charged sites (‐SO 3 − /TFSA −1 ) for efficient transport (Scheme b).…”

Section: Methodsmentioning

confidence: 99%

A Metal–Organic Framework Impregnated with a Binary Ionic Liquid for Safe Proton Conduction above 100 °C

Sun

Wen

Chen

et al. 2016

Chemistry A European J

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To develop proton-conducting materials under low-humidity conditions and at moderate working temperature still remains challenging for fuel-cell technology. Here, a new type of proton-conducting material, EIMS-HTFSA@MIL, which was prepared by impregnating the binary ionic liquid, EIMS-HTFSA (EIMS=1-(1-ethyl-3-imidazolium)propane-3-sulfonate; HTFSA=N,N-bis(trifluoromethanesulfonyl)amide), into a mesoporous metal-organic framework, MIL-101 ([Cr F(H O) O(BDC) ⋅n H O] (n≈0.25, BDC=1,4-benzenedicarboxylate)) is reported. By taking advantage of the ionic-liquid properties, such as high thermal stability, non-volatility, non-flammability, and low corrosivity, EIMS-HTFSA@MIL shows potential application as a safe electrolyte in proton conduction above 100 °C.

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Section: Methodsmentioning

confidence: 99%

A Metal–Organic Framework Impregnated with a Binary Ionic Liquid for Safe Proton Conduction above 100 °C

Sun

Wen

Chen

et al. 2016

Chemistry A European J

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“…(Model 3 is inspired by the high bond formation energies found in the quantum mechanics calculations for Tf2NH dimers.) 25 In Table 4, we show the results obtained for the dendrimer size for these three models. Differences between the models are small.…”

Section: ■ Models and Methodsmentioning

confidence: 99%

Molecular Dynamics Simulations of the Protonated G4 PAMAM Dendrimer in an Ionic Liquid System

2013

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Molecular dynamics simulations have been carried out for the ionic liquid system constituted by totally protonated PAMAM-EDA cations and Tf2N(-) anions. The conformational characteristics of the PMAM dendrimer (particularly the density profile around the dendrimer center) are compared with those obtained for the same dendrimer in water. We also investigate other features, such as the location of anions relative to the dendrimer molecules, and the interpenetration of the dendrimer cations in the ionic liquid system. It is shown that a substantial amount of anions are present in the outer part of the dendrimer, screening repulsive contacts between different cation molecules and favoring ionic conductivity. Dendrimer cations in the ionic liquid exhibit a significant degree of overlap.

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“…Introduction of the second strong electron acceptor at the nitrogen atom results in a further increase of acidity so that trifluoro‐ N ‐(2‐phenylacetyl)methanesulfonamide CF 3 SO 2 NHC(O)CH 2 Ph is ~5 p K a units more acidic (p K a 5.45 in methanol). Even more acidic is bis(trifluoromethanesulfonyl)imide (CF 3 SO 2 ) 2 NH for which p K a in MeOH is as low as 2.7 . The formation of hydrogen‐bonded complexes of N ‐methyltrifluoromethanesulfonamide with protophilic solvents was studied by us earlier …”

Section: Introductionmentioning

confidence: 99%

The basicity of sulfonamides and carboxamides. Theoretical and experimental analysis and effect of fluorinated substituent

Shainyan

Chípanina

Oznobikhina

2012

J of Physical Organic Chem

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The basicity of a series of sulfonamides and carboxamides with respect to protonation and hydrogen-bonded complex formation with phenol was investigated by calculations using the Becke three-parameter hybrid functional combined with Lee-Yang-Parr correlation functional with the 6-311G** and 6-311++G** basis sets and by infrared spectroscopy. The effect of fluorinated substituent was studied for the two series. The proton affinity of nitrogen in sulfonamides is higher than oxygen, in contrast to carboxamides, which are protonated at oxygen. The phenyl group in benzenesulfonamide increases the basicity of both heteroatoms, but more strongly of the nitrogen, whereas in benzamide the effect on the two heteroatoms is about the same. The CF 3 group equally decreases the basicity of nitrogen and oxygen atoms in sulfonamides and carboxamides. The second fluorinated substituent decreases the basicity of oxygen in (CF 3 CO) 2 NH more strongly than of nitrogen. For sulfonamides, the same effect results in the reverse of the center of basicity from nitrogen in (MeSO 2 ) 2 NH to oxygen in (CF 3 SO 2 ) 2 NH. All studied carboxamides give H-complexes via the carbonyl oxygen, whereas for sulfonamides two types of H-complexes, with the OHÁÁÁN and OHÁÁÁO=S, were found theoretically, the latter being more stable. The exception is bisimide (CF 3 SO 2 ) 2 NH, for which only the OHÁÁÁO=S complex is stable. Experimentally, only the oxygen-bound complexes are observed. Analysis of the natural charges revealed an 'abnormal' increase of the electron density on the NH group by electron-acceptor substituents in CF 3 SO 2 NHR, which was explained using the natural bond orbital analysis by loosening of the S-N bond because of orbital interactions with the s* SÀN orbital.

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Structure of bis(trifluoromethanesulfonyl)imide in inert and protophilic media

Cited by 15 publications

References 26 publications

A Metal–Organic Framework Impregnated with a Binary Ionic Liquid for Safe Proton Conduction above 100 °C

A Metal–Organic Framework Impregnated with a Binary Ionic Liquid for Safe Proton Conduction above 100 °C

Molecular Dynamics Simulations of the Protonated G4 PAMAM Dendrimer in an Ionic Liquid System

The basicity of sulfonamides and carboxamides. Theoretical and experimental analysis and effect of fluorinated substituent

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