IR Spectra of Trifluoromethanesulfonamide and Its Self-Associates in the Gas Phase

Chípanina, N. N.; Sherstyannikova, L. V.; Danilevich, Yu. S.; Turchaninov, V. K.; Shainyan, B. А.

doi:10.1023/b:rugc.0000031861.73702.f5

Russian Journal of General Chemistry

2004

DOI: 10.1023/b:rugc.0000031861.73702.f5

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IR Spectra of Trifluoromethanesulfonamide and Its Self-Associates in the Gas Phase

N. N. Chípanina

L. V. Sherstyannikova

Yu. S. Danilevich

et al.

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Cited by 16 publications

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“…The n(NH) values measured in these solvents do not obey regression equations (2) and (3). Both bands of amide I are strongly broadened, which suggests coexistence of several types of associates.…”

mentioning

confidence: 87%

“…(3). Inclusion of the n as (NH 2 ) and n s (NH 2 ) frequencies of the monomer measured in CHCl 3 and 3400 3500 3600 n, cm !1 (4) and (5) compared to (2) and (3):…”

mentioning

confidence: 96%

“…An equilibrium between the monomeric molecules of amide I and its self-associates Ia3If (Scheme 1) gives rise to a complex pattern in the range 3000 3 4000 cm !1 with a set of overlapping bands, even in the gas phase [2].…”

mentioning

confidence: 99%

“…In low-polarity CCl 4 and C 2 Cl 4 , a cyclic tetramer is formed, in which the NH 2 group is involved in two NH...O=S hydrogen bonds; in moderately polar CHCl 3 , the compound forms cyclic trimers in which one of the hydrogen atoms of the NH 2 group is not involved in hydrogen bonding; in highly polar C 2 HCl 5 and C 2 H 4 Cl 2 , the compound forms chain-like dimers.Trifluoromethanesulfonamide and N-methyltrifluoromethanesulfonamide exhibit high acidity (pK a 6.39 and 7.56, respectively [1]) and undergo reversible self-association in the gas phase at 3853 458 K, forming various oligomeric species [2,3]. In inert solvents, N-methyltrifluoromethanesulfonamide forms cyclic and chain-like dimers [3]; their relative content is determined by the strength of the NH...O=S hydrogen bond and by the energy of nonspecific solvation.…”

mentioning

confidence: 99%

“…Trifluoromethanesulfonamide and N-methyltrifluoromethanesulfonamide exhibit high acidity (pK a 6.39 and 7.56, respectively [1]) and undergo reversible self-association in the gas phase at 3853 458 K, forming various oligomeric species [2,3]. In inert solvents, N-methyltrifluoromethanesulfonamide forms cyclic and chain-like dimers [3]; their relative content is determined by the strength of the NH...O=S hydrogen bond and by the energy of nonspecific solvation.…”

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confidence: 99%

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Self-Association of Trifluoromethanesulfonamide in Inert Solvents

et al. 2005

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Trifluoromethanesulfonamide exists in inert solvents as an equilibrium mixture of the monomer and self-associates of the structure depending on the solvent polarity. In low-polarity CCl 4 and C 2 Cl 4 , a cyclic tetramer is formed, in which the NH 2 group is involved in two NH...O=S hydrogen bonds; in moderately polar CHCl 3 , the compound forms cyclic trimers in which one of the hydrogen atoms of the NH 2 group is not involved in hydrogen bonding; in highly polar C 2 HCl 5 and C 2 H 4 Cl 2 , the compound forms chain-like dimers.Trifluoromethanesulfonamide and N-methyltrifluoromethanesulfonamide exhibit high acidity (pK a 6.39 and 7.56, respectively [1]) and undergo reversible self-association in the gas phase at 3853 458 K, forming various oligomeric species [2,3]. In inert solvents, N-methyltrifluoromethanesulfonamide forms cyclic and chain-like dimers [3]; their relative content is determined by the strength of the NH...O=S hydrogen bond and by the energy of nonspecific solvation. Data on the structure of N-unsubstituted perfluoroalkanesulfonamides in solutions are lacking. Less acidic methanesulfonamide (pK a 10.8 [1]) exists in dilute CCl 4 solutions in the form of monomeric molecules [4].In this study we examined experimentally and theoretically the self-association of perfluoroalkanesulfonamides CF 3 SO 2 NH 2 (I), C 2 F 5 SO 2 NH 2 (II), and CF 3 SO 2 NHCH 3 (III) in inert aprotic solvents and in protophobic chloroform, and also the effect of the solvent polarity on the structure of the associates. For this purpose, we used IR spectroscopy, dielectrometry, and DFT B3LYP/6-31G* calculations.Various self-associates of amides I3III are formed via NH...O=S hydrogen bonds of various strengths; therefore, as the parameter characterizing the structure of the associates we used the stretching vibration frequencies of the free and bonded NH groups. An equilibrium between the monomeric molecules of amide I and its self-associates Ia3If (Scheme 1) gives rise to a complex pattern in the range 3000 3 4000 cm !1 with a set of overlapping bands, even in the gas phase [2].Generally, these bands can belong to the stretching vibrations of free NH 2 groups (monomers Ia and Ia`; chain-like dimer Ic), NH 2 groups fully involved in hydrogen bonding (tetramer If), and those containing one free NH group (dimer Ib; trimers Id and Ie). Amide III, according to our previous study [3], in low-polarity CCl 4 exists in the form of monomer IIIa and cyclic dimer IIIb, and in more polar CH 2 Cl 2 , in the form of chain-like dimers IIIc having a higher dipole moment (Scheme 2) [3].The energy of the NH...O=S hydrogen bond, according to quantum-chemical calculations, only slightly depends on the structure of the self-associates and is approximately equal to 26 kJ mol !1 per bond. The experimentally determined enthalpy of formation of chain-like dimer IIIc is 20 kJ mol !1 [5].We estimated in this study the enthalpy of formation (DH) of cyclic dimer IIIb in CCl 4 by the procedure applied in [5] to chain-like dimer IIIc and based on measuring t...

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mentioning

confidence: 87%

“…(3). Inclusion of the n as (NH 2 ) and n s (NH 2 ) frequencies of the monomer measured in CHCl 3 and 3400 3500 3600 n, cm !1 (4) and (5) compared to (2) and (3):…”

mentioning

confidence: 96%

mentioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

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Self-Association of Trifluoromethanesulfonamide in Inert Solvents

et al. 2005

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Trifluoromethanesulfonamide: X-ray single-crystal determination and quantum chemical calculations

Sterkhova

Shainyan

2015

J. Phys. Org. Chem.

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The X-ray single-crystal structure of 1,1,1-trifluoromethanesulfonamide (triflamide) CF 3 SO 2 NH 2 , which is the ancestor of a large family of its derivatives, has been determined. The crystal structure is composed of infinite layers with an interlayer distance of 3.4 Å. Geometry optimization at the Møller-Plesset (MP2) and density functional theory (DFT) level showed the calculated bond distances to be, as a rule, longer than the experimental ones. A trial to simulate crystal packing effect on the geometrical parameters by calculating the dimer of triflamide in the gas phase failed -the starting X-ray geometry of the 'dimeric' unit with one NH···O=S H-bond -was optimized to the cyclic dimer with two H-bonds. However, when the external (crystal) field effect was simulated using the polarizable continuum model, the experimental geometry of the 'dimeric' fragment was satisfactorily reproduced. Calculations of the heptamer cluster having the structure of the hexagon with six triflamide molecules in vertices and one in the middle nicely reproduce the X-ray structure and brings the geometrical parameters closer to the experiment.

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Acid‐base properties and supramolecular structure of N‐[(hydroxymethyl)triazolyl]triflamides: DFT, ab initio, and FTIR study

Shainyan

Chípanina

Oznobikhina

et al. 2016

J of Physical Organic Chem

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For N‐{[2‐(hydroxymethyl)‐2H‐1,2,3‐triazolyl‐4‐yl]methyl}triflamide 1, N‐{[2‐(hydroxymethyl)‐2H‐1,2,3‐triazolyl‐4‐yl]methyl}‐N‐phenyltriflamide 2, and N,N‐bis{[2‐(hydroxymethyl)‐2H‐1,2,3‐triazolyl‐4‐yl]methyl}triflamide 3, the proton affinities of the triazole nitrogen atoms and the hydroxy and sulfonyl oxygen atoms as well as the energies of formation of the conformers with intramolecular H‐bonds and dimers with intermolecular NH⋯N, OH⋯N, OH⋯O═S, and NH⋯O═S H‐bonds were calculated by density functional theory and second‐order Møller‐Plesset perturbation methods. Quantum Theory of Atoms in Molecules analysis was performed to investigate the nature of H‐bonds. According to Fourier transform infrared spectroscopy, in CH2Cl2 solution, the monomeric molecules of 1 to 3 exist in the equilibrium with cyclic dimers having the OH⋯N hydrogen bonds.

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IR Spectra of Trifluoromethanesulfonamide and Its Self-Associates in the Gas Phase

Cited by 16 publications

References 5 publications

Self-Association of Trifluoromethanesulfonamide in Inert Solvents

Self-Association of Trifluoromethanesulfonamide in Inert Solvents

Trifluoromethanesulfonamide: X-ray single-crystal determination and quantum chemical calculations

Acid‐base properties and supramolecular structure of N‐[(hydroxymethyl)triazolyl]triflamides: DFT, ab initio, and FTIR study

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