Intramolecular H-Bonds: DFT and QTAIM Studies on 3-(Aminomethylene)pyran-2,4-dione and Its Derivatives

Grabowski, Sławomir J.; Małecka, Magdalena

doi:10.1021/jp064997p

Cited by 48 publications

(48 citation statements)

References 64 publications

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“…It was revealed that electron density at the H-bond BCP may be treated as a measure of hydrogen bond strength [95][96][97][98]. The parameters of the ring critical point RCP (Figure 4) may also be considered as descriptors of hydrogen bond strength [99]. Correlations between the characteristics of RCPs and other parameters describing H-bond strength were observed by Alkorta [100,101].…”

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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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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“…This shows that the Espinosa’s approach [49, 50] is applicable also in cases of other than originally developed for interactions (OH · · · O, NH · · · O, CH · · · F, FH · · · F, FH · · · N) [54–57]. This has also been shown for other interactions including intramolecular hydrogen bonding [58] and the negatively charged species as oxyanions [18] or π-H · · · O contacts [59]. …”

Section: Resultsmentioning

confidence: 77%

Substituent effects in hydrogen bonding: DFT and QTAIM studies on acids and carboxylates complexes with formamide

Ośmiałowski

2014

J Mol Model

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Four series of hydrogen bonded complexes of formamide and substituted benzoic acids and benzoates were studied in the light of substituent effect on intermolecular interactions. The analysis based on energy of interaction, geometry, QTAIM-derived properties of hydrogen bond critical point and energy of hydrogen bonds were made and discussed. The opposite effect of the substituent on hydrogen bond donor and acceptor in acid series was found and analyzed. The isodesmic reactions were used to further study the interaction preferences.FigureᅟElectronic supplementary materialThe online version of this article (doi:10.1007/s00894-014-2356-8) contains supplementary material, which is available to authorized users.

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“…However, systems with the negative H BCP value and positive ! 2 q(r BCP ) are more common and they are often analyzed [27]. In this regard, our data in Table II, illustrate that Laplacians and H BCP values are positive (for HÁÁÁN contact), indicating partially covalent interaction.…”

Section: Charge Density Propertiesmentioning

confidence: 70%

Theoretical study of the effects of substitution, solvation, and structure on the interaction between nitriles and methanol

Raissi

Farzad

Nadim

et al. 2011

Int J of Quantum Chemistry

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OH) complexes using density functional theory. The calculations were conducted on B3LYP/6-311þþG** level of theory for optimization of geometries of complexes and monomers. An improper hydrogen bonding (HB) in the H 3 COAHÁÁÁNCAR complexes was observed in that N atom of the nitriles functions acts as a proton acceptor. Furthermore, quantum theory of ''Atoms in Molecules'' (AIM) and natural bond orbital (NBO) method were applied to analyze H-bond interactions in respective complexes. The electron density (q) and Laplacian (! 2 q) properties, estimated by atoms in molecules calculations, indicate that HÁÁÁN bond possesses low q and positive ! 2 q values, which are in agreement with partially covalent character of the HBs, whereas OAH bonds have negative ! 2 q values. In addition, the weak intermolecular force due to dipole-dipole interaction (U) is also considered for analysis. The examination of HB in these complexes by quantum theory of NBO method fairly supports the ab initio results. Natural population analysis data, the electron density, and Laplacian properties, as well as, the m(OAH) and c(OAH) frequencies of complexes, calculated at the B3LYP/6-311þþG** level of theory, are used to evaluate the HB interactions. The calculated geometrical parameters and conformational analysis in water phase solution show that the H 3 COAHÁÁÁNCAR complexes in water are more stable than that in gas phase. The obtained results demonstrated a strong influence of

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Intramolecular H-Bonds: DFT and QTAIM Studies on 3-(Aminomethylene)pyran-2,4-dione and Its Derivatives

Cited by 48 publications

References 64 publications

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

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

Substituent effects in hydrogen bonding: DFT and QTAIM studies on acids and carboxylates complexes with formamide

Theoretical study of the effects of substitution, solvation, and structure on the interaction between nitriles and methanol

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