AIM Analysis of Intramolecular Hydrogen Bonding in<i>O</i>-Hydroxy Aryl Schiff Bases

Filarowski, Aleksander; Majerz, Irena

doi:10.1021/jp076253x

Cited by 60 publications

(41 citation statements)

References 113 publications

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“…[37,[39][40][41]. H-bond dissociation energies of stable OH and NH form (at the sixteenth step) of the title compound are approximately found as 12 kcal/mol and these values are comparable the corresponding values obtained for o-hydroxy aryl Schiff bases reported in [45]. Considering only the distances between the donor and acceptor atom, it can be stated that intramolecular H-bonds in the title compound at both the temperatures can be regarded as low-barrier hydrogen bonds (LBHB), since the corresponding distances of O-HÁÁÁN (or OÁÁÁH-N)-type LBHBs are less than 2.65 Å [37].…”

Section: Computational Studysupporting

confidence: 84%

The proton transfer process observed in the structure analysis and DFT calculations of (E)-2-ethoxy-6-[(2-methoxyphenylimino)methyl]phenol

et al. 2010

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The crystal and molecular structures of an o-hydroxy Schiff base derivative, (E)-2-ethoxy-6-[(2-methoxyphenylimino)methyl]phenol, have been determined by single crystal X-ray diffraction analyses at 296 and 100 K. The results from temperature-dependent structural analysis regarding the tautomeric equilibrium of the compound were interpreted with the aid of quantum chemical calculations. To clarify the tautomerization process and its effects on the molecular geometry, the gasphase geometry optimizations of two possible tautomers of the title molecule, its OH and NH form, were achieved using DFT calculations with B3LYP method by means of 6-31 ? G(d,p) basis set. In order to describe the potential barrier belonging to the phenolic proton transfer, nonadiabatic Potential Energy Surface (PES) scan was performed based on the optimized geometry of the OH tautomeric form by varying the redundant internal coordinate, O-H bond distance. The Harmonic Oscillator Model of Aromaticity (HOMA) indices were calculated in every step of the scan process so as to express the deformation in the aromaticities of principal molecular moieties of the compound. The results show that there is a dynamic equilibrium between the aromaticity level of phenol and chelate ring and furthermore p-electron coupling affecting overall molecule of the title compound. Charge transfer from phenol ring to pseudo-aromatic chelate ring increases with increasing temperature, whereas p-electron transfer from chelate ring to anisole ring is decreased as temperature increases. The most strength intramolecular H-bonds are observed for conformers close to transition state.

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Section: Computational Studysupporting

confidence: 84%

The proton transfer process observed in the structure analysis and DFT calculations of (E)-2-ethoxy-6-[(2-methoxyphenylimino)methyl]phenol

et al. 2010

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“…The obtained HB energy values were converted from atomic unit to kilo calorie per mole with the conversion factor, 627.5095. Espinosa's approach has been used to find the IMHB strength satisfactorily and introduced as a reliable method [38]. QTAIM is a powerful tool based on the topology of charge density that presents a clear definition of an atom and perfectly describes a chemical bond.…”

Section: Computational Detailsmentioning

confidence: 99%

Computational investigation on the intramolecular resonance-inhibited hydrogen bonding: a new type of interaction versus the RAHB model

Masumian

Nowroozi

2015

Theor Chem Acc

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“…AIM methodology has been applied to exclude or confirm the existence of intramolecular hydrogen bonds [102][103][104][105][106]. In an earlier study of the spectroscopic properties of pyrrole-2-carbaldehyde, the formation of intramolecular interactions C=O … H-N was proposed [30].…”

Section: Aim Studiesmentioning

confidence: 99%

Conformational Preferences of 2-Acylpyrroles in Light of FT-IR and DFT Studies

Dubis

2014

J Phys Chem Biophys

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2-carboxylic acids [3] and corresponding esters [4]. Pyrrole-2-carboxylates are also useful substrates for the preparation of more complex pyrrole containing systems [5] such as ketorolac, a drug with anti-inflammatory and analgesic properties [6]. It is noted that the 2-acylpyrrole motif is widespread in nature. There are many examples of 2-acylpyrrole based molecules (Figure 1) with various biological activities [7,8]. Representative examples are pyoluteorin and pyrrolomycin D, secondary metabolites produced by marine Conformational Preferences of 2-Acylpyrroles in Light of FT-IR and DFT StudiesAlina T Dubis* Institute of Chemistry, University of Białystok, Hurtowa 1, Poland AbstractConformations of alpha-substituted pyrroles have been effectively studied using spectroscopic methods assisted by theoretical calculations developed in the recent decade. The question of how to effectively study the conformation of 2-acylpyrrole no longer remains unanswered. The detailed spectroscopic studies conducted in the last decade and interpreted on the basis of theoretical calculations provide a satisfactory answer to that question. Based on the Density Functional Theory (DFT) calculations of conformational properties of 2-acylpyrroles, for which two stable rotameric forms were predicted, syn and anti-conformers have been studied either by experimental or theoretical methods. The family of 2-acylpyrroles have both a proton donor N-H group and a proton acceptor C=O group. This structure favors the formation of doubly hydrogen-bonded cyclic dimers connected by two N-H...O=C bonds. The tendency to form cyclic dimers stabilizes the syn-conformation. Due to these properties 2-acylpyrroles can be used as structural models for the conformational analysis of peptides.This review summarizes recent investigations of conformations of 2-acylpyrroles, with a particular emphasis on the hydrogen bonds forming within these systems. The influence of 2-substitution on different aspects of stability of these molecular systems and the usefulness of infrared spectroscopy supported by theoretical calculations in H-bonds and conformational studies are discussed. Among the molecular properties hydrogen bond energy, structural characteristics such as C=O bond length of dimers and unique spectral features of 2-acylpyrroles that can be used to predict and investigate the conformation and structure of proteins are considered.Graphical abstract. The potential energy diagram of 2-acylpyrroles as a function of the dihedral angle pyrrole ringcarbonyl group of bond rotation. Most stable conformer syn converts to conformer anti via the transition state TS1; less stable conformer anti converts to conformer syn via the transition state TS2. conformational research and can greatly support experimental work with quite good accuracy. Among the most useful parameters are geometrical parameters, relative conformational energies, barriers to internal rotation and vibrational frequencies for each conformer. Journal of Physical Chemistry & BiophysicsEnergy differ...

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AIM Analysis of Intramolecular Hydrogen Bonding inO-Hydroxy Aryl Schiff Bases

Cited by 60 publications

References 113 publications

The proton transfer process observed in the structure analysis and DFT calculations of (E)-2-ethoxy-6-[(2-methoxyphenylimino)methyl]phenol

The proton transfer process observed in the structure analysis and DFT calculations of (E)-2-ethoxy-6-[(2-methoxyphenylimino)methyl]phenol

Computational investigation on the intramolecular resonance-inhibited hydrogen bonding: a new type of interaction versus the RAHB model

Conformational Preferences of 2-Acylpyrroles in Light of FT-IR and DFT Studies

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