Thermodynamics of the hydrogen bonding of nitrogen-containing cyclic and aromatic compounds with proton donors: The structure-property relationship

Rakipov, Ilnaz T.; Varfolomeev, Mikhail A.; Kirgizov, A. Yu.; Solomonov, Boris N.

doi:10.1134/s0036024414120255

Cited by 15 publications

(4 citation statements)

References 32 publications

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“…The

parameter was calculated from the linear dependences of solution enthalpies of n-alkanes in solvents against the characteristic volume of n-alkanes. The detailed description of the approach and the examples of determining the contributions of non-specific intermolecular interactions of different solutes in solvents are presented in earlier works [ 14 , 15 , 22 , 29 , 30 , 31 , 32 ]. The specific relative cavity formation enthalpies of cyclohexane and benzene are 5.02 10 2 kJ∙cm −3 and 1.42∙10 2 kJ∙cm −3 [ 23 ], respectively.…”

Section: Resultsmentioning

confidence: 99%

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Thermochemistry of Solution, Solvation, and Hydrogen Bonding of Cyclic Amides in Proton Acceptor and Donor Solvents. Amide Cycle Size Effect

et al. 2021

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In the present work, the thermochemistry of solution, solvation, and hydrogen bonding of cyclic amides in proton acceptor (B) and proton donor (RXH) solvents were studied. The infinite dilution solution enthalpies of δ-valerolactam, N-methylvalerolactam, ε-caprolactam, and N-methylcaprolactam were measured at 298.15 K. The solvation enthalpies of cyclic amides were calculated based on the measured solution enthalpies and sublimation/vaporization enthalpies from literature. The enthalpies of hydrogen bonding between cyclic amides and proton acceptor and donor solvents were then calculated as a difference between the total solvation enthalpy and the non-specific contribution. The latter was estimated via two different approaches in proton donor and proton accepting solvents. The effect of the cycle size on the strength of hydrogen bonding of the cyclic amides in solution is discussed.

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“…The

Section: Resultsmentioning

confidence: 99%

“…The calorimeters were tested by the dissolution of potassium chloride and 1-propanol in water [ 19 , 20 ]. The calorimeter and the measurement procedure were described in works [ 21 , 22 ]. The enthalpies of solution of cyclic amides in solvent obtained in work are collected in Supplementary Material ( Table S2 and Table S3 ).…”

Section: Experimental Partmentioning

confidence: 99%

Thermochemistry of Solution, Solvation, and Hydrogen Bonding of Cyclic Amides in Proton Acceptor and Donor Solvents. Amide Cycle Size Effect

et al. 2021

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“…As in excess chloroform (used as the solvent), the non-solvated species (Amac)SiMe 2 and free NMI appear unlikely (in the latter case, experimental thermochemical studies revealed the exothermal dissolution of NMI in chloroform [41]); we consider the solvates (Amac)SiMe 2 -CHCl 3 and NMI-CHCl 3 as more relevant starting materials involved in further reactions such as the formation of compounds (Amac)SiMe 2 -NMI-CHCl 3 . Therefore, instead of the formation of (Amac)SiMe 2 -NMI-CHCl 3 out of the three individual components and (Amac)SiMe 2 + NMI + CHCl 3 (associated with changes in energy up to −18.6 kcal•mol −1 and in Gibbs free energy up to 10.9 kcal•mol −1 , which can thus be expected to be slightly exergonic upon correction by ca.…”

Section: Tablementioning

confidence: 99%

“…For example, even in case of the simple molecule NMI, further solvation with chloroform (which exceeds the 1:1 adduct formation) may be considered to contribute. Rakipov et al attributed the pronounced exothermal reaction of NMI and chloroform to the 1:2 solvate formation in chloroform-rich solution [41].…”

Section: Tablementioning

confidence: 99%

Lewis Acid-Base Adducts of α-Amino Acid-Derived Silaheterocycles and N-Methylimidazole

Seidel,

Gericke,

Kutzner

et al. 2023

Molecules

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In chloroform solution, the reaction of bis(tert-butylamino)dimethylsilane ((tBuNH)2SiMe2) and an α-amino acid (α-amino isobutyric acid, H2Aib; D-phenylglycine, H2Phg; L-valine, H2Val) in the presence of N-methylimidazole (NMI) gave rise to the formation of the pentacoordinate silicon complexes (Aib)SiMe2-NMI, (Phg)SiMe2-NMI and (Val)SiMe2-NMI, respectively. Therein, the amino acid building block was a di-anionic bidentate chelator at the silicon atom. In solution, the complexes were involved in rapid coordination–dissociation equilibria between the pentacoordinate Si complex (e.g., (Aib)SiMe2-NMI) and its constituents NMI and a five-membered silaheterocycle (e.g., (Aib)SiMe2), as shown by 29Si NMR spectroscopy. The energetics of the Lewis acid-base adduct formation and the competing solvation of the NMI molecule by chloroform were assessed with the aid of computational methods. In CDCl3 solution, deuteration of the silaheterocycle NH group proceeded rapidly, with more than 50% conversion within two days. Upon cooling to −44 °C, the chloroform solvates of the adducts (Aib)SiMe2-NMI and (Phg)SiMe2-NMI crystallized from their parent solutions and allowed for their single-crystal X-ray diffraction analyses. In both cases, the Si atom was situated in a distorted trigonal bipyramidal coordination sphere with equatorial Si–C bonds and an equatorial Si–N bond (the one of the silaheterocycle). The axial positions were occupied by a carboxylate O atom of the silaheterocycle and the NMI ligand’s donor-N-atom.

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Thermochemistry of Solutions of Alkanes in Binary Mixtures: Azeotropes

et al. 2020

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Thermodynamics of the hydrogen bonding of nitrogen-containing cyclic and aromatic compounds with proton donors: The structure-property relationship

Cited by 15 publications

References 32 publications

Thermochemistry of Solution, Solvation, and Hydrogen Bonding of Cyclic Amides in Proton Acceptor and Donor Solvents. Amide Cycle Size Effect

Thermochemistry of Solution, Solvation, and Hydrogen Bonding of Cyclic Amides in Proton Acceptor and Donor Solvents. Amide Cycle Size Effect

Lewis Acid-Base Adducts of α-Amino Acid-Derived Silaheterocycles and N-Methylimidazole

Thermochemistry of Solutions of Alkanes in Binary Mixtures: Azeotropes

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