Theoretical Studies of Hydrogen Bond Interactions in Fluoroacetic Acid Dimer

Chermahini, Alireza Najafi; Mahdavian, Mohsen; Teimouri, Abbas

doi:10.5012/bkcs.2010.31.04.941

Cited by 8 publications

(6 citation statements)

References 35 publications

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“…The prototype in this case is α-fluoroacetic acid. Chermahini et al , [ 172 ] found four local-energy-minimum structures for this molecule in the gas phase by ab initio and DFT calculations. All molecules show slightly distorted C S symmetry, thus the heavy atoms are almost co-planar.…”

Section: Conformational Equilibriamentioning

confidence: 99%

Competing Intramolecular vs. Intermolecular Hydrogen Bonds in Solution

Nagy

2014

IJMS

151

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A hydrogen bond for a local-minimum-energy structure can be identified according to the definition of the International Union of Pure and Applied Chemistry (IUPAC recommendation 2011) or by finding a special bond critical point on the density map of the structure in the framework of the atoms-in-molecules theory. Nonetheless, a given structural conformation may be simply favored by electrostatic interactions. The present review surveys the in-solution competition of the conformations with intramolecular vs. intermolecular hydrogen bonds for different types of small organic molecules. In their most stable gas-phase structure, an intramolecular hydrogen bond is possible. In a protic solution, the intramolecular hydrogen bond may disrupt in favor of two solute-solvent intermolecular hydrogen bonds. The balance of the increased internal energy and the stabilizing effect of the solute-solvent interactions regulates the new conformer composition in the liquid phase. The review additionally considers the solvent effects on the stability of simple dimeric systems as revealed from molecular dynamics simulations or on the basis of the calculated potential of mean force curves. Finally, studies of the solvent effects on the type of the intermolecular hydrogen bond (neutral or ionic) in acid-base complexes have been surveyed.

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Section: Conformational Equilibriamentioning

confidence: 99%

Competing Intramolecular vs. Intermolecular Hydrogen Bonds in Solution

Nagy

2014

IJMS

151

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“…Therefore, bond path is an universal indicator of bonded interactions . Accordingly, QTAIM has become a method that has already been successfully applied to understand conventional hydrogen bonds, , C–H···O bonds, and dihydrogen bonds. , …”

Section: Introductionmentioning

confidence: 99%

Hydrogen–Hydrogen Bonds in Highly Branched Alkanes and in Alkane Complexes: A DFT, ab initio, QTAIM, and ELF Study

Monteiro

Firme

2014

J. Phys. Chem. A

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The hydrogen-hydrogen (H-H) bond or hydrogen-hydrogen bonding is formed by the interaction between a pair of identical or similar hydrogen atoms that are close to electrical neutrality and it yields a stabilizing contribution to the overall molecular energy. This work provides new, important information regarding hydrogen-hydrogen bonds. We report that stability of alkane complexes and boiling point of alkanes are directly related to H-H bond, which means that intermolecular interactions between alkane chains are directional H-H bond, not nondirectional induced dipole-induced dipole. Moreover, we show the existence of intramolecular H-H bonds in highly branched alkanes playing a secondary role in their increased stabilities in comparison with linear or less branched isomers. These results were accomplished by different approaches: density functional theory (DFT), ab initio, quantum theory of atoms in molecules (QTAIM), and electron localization function (ELF).

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“…To further quantitatively explore these hydrogen bonding and electrostatic interactions between substrate and DMF and/or DBU (DBU‐H + ), we performed natural bond orbital (NBO) second‐order perturbation interaction energy analysis for transition states TS 4‐5 , TS 8c‐9c , and TS 11c‐12c (Supporting Information Table S3). The calculated results suggest that the total stabilization energies amount to 28.87 (substrates and DBU‐H + ) and 2.81 kcal/mol (DMF and DBU‐H + ) in transition state TS 4‐5 , respectively.…”

Section: Resultsmentioning

confidence: 99%

“…To further quantitatively explore these hydrogen bonding and electrostatic interactions between substrate and DMF and/ or DBU (DBU-H 1 ), we performed natural bond orbital (NBO) second-order perturbation interaction energy [28][29][30] analysis for transition states TS 4-5 , TS 8c-9c , and TS 11c-12c (Supporting Information Table S3). [4][5] , respectively.…”

mentioning

confidence: 99%

The multieffects of DMF and DBU on the [5 + 1] benzannulation of nitroethane and α‐alkenoyl ketene‐(S,S)‐acetals: Hydrogen bonding and electrostatic interactions

Yuan

Zheng

et al. 2015

J Comput Chem

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A density functional theory (DFT) study was performed to elucidate the mechanism for the [5 + 1] benzannulation of nitroethane and α-alkenoyl ketene-(S,S)-acetals. The calculation results are consistent with experimental findings, showing that the reaction proceeds via deprotonation of nitroethane, nucleophilic addition, intramolecular cyclization, elimination of HNO2 , and the keto-enol tautomerization sequence. It was disclosed that N,N-dimethylformamide (DMF) and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) act as not only solvent and nonnucleophilic base, respectively, but also catalysts in the reaction by stabilizing the transition states (TSs) and intermediates via intermolecular hydrogen bonds and electrostatic interactions. Besides, the effective orbital interaction of the reaction site in TS also contributes to the intramolecular cyclization step. The new mechanistic insights obtained by DFT calculations highlight that the hydrogen bonds and electrostatic interactions are key factors for the [5 + 1] benzannulation of nitroethane and α-alkenoyl ketene-(S,S)-acetals.

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Theoretical Studies of Hydrogen Bond Interactions in Fluoroacetic Acid Dimer

Cited by 8 publications

References 35 publications

Competing Intramolecular vs. Intermolecular Hydrogen Bonds in Solution

Competing Intramolecular vs. Intermolecular Hydrogen Bonds in Solution

Hydrogen–Hydrogen Bonds in Highly Branched Alkanes and in Alkane Complexes: A DFT, ab initio, QTAIM, and ELF Study

The multieffects of DMF and DBU on the [5 + 1] benzannulation of nitroethane and α‐alkenoyl ketene‐(S,S)‐acetals: Hydrogen bonding and electrostatic interactions

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