A spectroscopic study of the strength of the hydrogen bonding in systems consisting of a tetraalkylphosphonium salt and an alcohol

Boldeskul, I. E.; Egorov, Yu. P.; Makovetskii, Yu. P.; Ryl'tsev, E. V.; Feshchenko, N. G.

doi:10.1007/bf00607116

J Appl Spectrosc

1972

DOI: 10.1007/bf00607116

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A spectroscopic study of the strength of the hydrogen bonding in systems consisting of a tetraalkylphosphonium salt and an alcohol

I. E. Boldeskul¹,

Yu. P. Egorov²,

Yu. P. Makovetskii³

et al.

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2005

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“…Thus the classical procedure for determination of the thermodynamic parameters of a hydrogen bond from the temperature dependence of the optical density at the n(NH) free maximum [15] cannot be applied in our case. Therefore, we used the temperature dependence of the overall intensity of the bands corresponding to stretching vibrations of both free and associated NH groups [16,17]. As a basis we used Eqs.…”

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Energy of Formation of an Acyclic N-Methyltrifluoromethanesulfonamide Dimer

et al. 2005

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The energy of formation of an open-chain N-methyltrifluoromethanesulfonamide dimer stabilized by the N3H...O=S hydrogen bond is 20.1 kJ mol !1 (CH 2 Cl 2 ). This value exceeds by~12 kJ mol !1 the energy of formation of cyclic secondary methanesulfonamide self-associates per hydrogen bond.A specific property of trifluoromethanesulfonamide and its N-methyl derivative is their ability to form cyclic dimers in nonpolar inert solvents and in the gaseous phase [1,2]. According to the data of IR and Raman spectroscopy and electron diffraction, fluorosulfonic acid molecules in the gaseous phase and in solution also give rise to cyclic dimers [3,4]. The IR spectra of centrosymmetric dimers derived from secondary methanesulfonamides were discussed in [537]. Analogous structures formed by carboxylic acids were studied in detail in [8,9]. The heat of formation of carboxylic acid cyclic dimers reaches 40360 kJ mol !1 .N-Substituted carboxamides are involved in hydrogen bonding as s-cis or s-trans conformers. s-cis Conformers possess a stronger proton-donor ability, but s-trans conformers are more stable [10,11]. A combination of these factors determines the structure of self-associates, whether they are cyclic or open-chain dimers. The energy of self-association of carboxylic acid amides is also fairly high and is 15317 kJ mol !1 per hydrogen bond [8]. The corresponding energy found for secondary methanesulfonamides is 43 8 kJ mol !1 [5]. We anticipated that the energy of selfassociation of trifluoromethanesulfonamides per hydrogen bond should be considerably greater. Sulfonamides containing perfluoroalkyl groups exhibit a high acidity (pK a 6.39 [12] and 7.56 [13] for trifluoromethanesulfonamide and N-methyltrifluoromethanesulfonamide, respectively), and their cyclic dimers in the gas phase are stable up to 400 K. These data suggest formation of a fairly strong hydrogen bonds despite relatively weak electron-donor power of the S=O group in substituted methanesulfonamides [6,14]. In order to elucidate this problem, it is necessary to estimate the energy of hydrogen bond formation in different self-associates of trifluoromethanesulfonamides. The goal of the present work was to experimentally determine the energy of dimerization of N-methyltrifluoromethanesulfonamide (I) in an inert solvent by IR spectroscopy and to elucidate the dimer structure by quantum-chemical calculations in terms of the density functional theory (B3LYP) using 6-31G* and 6-311++G** basis sets.The energies of rotational isomers of compound I are almost similar (DE = 0.08 kJ mol !1 ), while its invertomers are degenerate [2]. Mutual orientation of the oxygen atoms in the SO 2 group and hydrogen atom on the nitrogen almost does not depend on the conformation. Therefore, the formation of either cyclic or open-chain dimers should be determined solely by the energy factors, i.e., by the strength of the N3H...O=S hydrogen bond and by the energy of nonspecific solvation. In fact, according to the IR data, compound I in carbon tetrachloride exists as an equilibriu...

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Energy of Formation of an Acyclic N-Methyltrifluoromethanesulfonamide Dimer

et al. 2005

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A spectroscopic study of the strength of the hydrogen bonding in systems consisting of a tetraalkylphosphonium salt and an alcohol

Cited by 1 publication

References 1 publication

Energy of Formation of an Acyclic N-Methyltrifluoromethanesulfonamide Dimer

Energy of Formation of an Acyclic N-Methyltrifluoromethanesulfonamide Dimer

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