&lt;b&gt;DFT calculations on 1,4-dithiine and S-oxygenated derivatives&lt;/b&gt;

Vessally, Esmail

doi:10.4314/bcse.v22i3.61259

Cited by 8 publications

(8 citation statements)

References 15 publications

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“…The geometric parameters of 1,4-dithiine obtained by a quantum chemical calculation (MP2 and B3LYP in the 6-311++G(d,p) basis set) well agree with the data of the calculation [7] and X-ray crystallography [3]. The DFT method showed a smaller discrepancy from the experimental data.…”

Section: Resultssupporting

confidence: 50%

“…Calculations were performed by MP2 and B3LYP methods using the Gaussian 98W program package [4]. It is worth noting that a number of authors have studied dithiine by quantum chemical methods [5,6], the latest and apparently most complete investigation being conducted by Vessally [7]. The ability of different cyclic molecules to conjugation and the formation of macrorings was examined by Gleiter [8].…”

Section: Introductionmentioning

confidence: 99%

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Quantum chemical estimation of the macrocyclization of 1,4-dithiine

2012

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Ab initio quantum chemical methods are employed to study the spatial and electronic structure of a 1,4-dithiine molecule. Calculations are performed with electron correlation treatment by MP2 and B3LYP methods in 6-311++G(d,p) and 6-311G basis sets. It is found that the macrocyclization of 1,4-dithiine is energetically favorable. The addition of each subsequent dithiine ring decreases the relative energy of the system by |0.5y2.3 kcal/mol. The cycle consisting of 7 dithiine rings is the most comfortable from the standpoint of the internal strain of the macrocycle. With an increase in the number of rings up to 10, the macrocycle starts to break into 4-, 5-, 6-, or 7-membered fragments. The formation of a nanotube based on a 7-membered macrocycle is energetically favorable. The inner diameter of this nanotube is 6.9 Å.

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Section: Resultssupporting

confidence: 50%

Section: Introductionmentioning

confidence: 99%

Quantum chemical estimation of the macrocyclization of 1,4-dithiine

2012

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“…In addition, geometries optimization and theoretical assignment of the IR, 1 H and 13 C NMR spectra of the H 2 L have been performed by using DFT method, which is widely used as a remarkable method in many areas of the computational chemistry [11][12][13][14][15][16][17][18][19][20].…”

Section: Introductionmentioning

confidence: 99%

N,N′-Dipyridoxyl(1,8-diamino-3,6-dioxaoctane) Schiff-base: Synthesis, experimental and theoretical identification

Beyramabadi¹,

Morsali²,

Bozorgmehr³

et al. 2013

Bull. Chem. Soc. Eth.

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ABSTRACT. The N,N′-dipyridoxyl(1,8-diamino-3,6-dioxaoctane) (=H2L) Schiff-base has been synthesized and characterized by IR, 1 H NMR, mass spectrometry and elemental analysis. Its optimized geometry and theoretical vibrational frequencies have been computed using density functional theory (DFT) method via the B3LYP functional. Also, its 1 H and 13 C NMR chemical shifts have been calculated at the same computational level. In optimized geometry of the H2L, the two pyridine rings are perpendicular to each other. The phenolic hydrogens are engaged in intramolecular-hydrogen bonds with the azomethine nitrogens.

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“…DFT calculations have shown that the S-oxygenated derivatives of 1,4-dithiine with one and two SO groups are puckered and have a shadow boat conformation[25]. Below we demonstrate that the puckering of these molecules and planarization of the systems with the SO 2 groups are due to enhancement and suppression of the PJTE.For this purpose we studied a series of six molecules: 1,4-dithiine and five its oxygenated derivatives.…”

mentioning

confidence: 65%

“…In other systems with planar reference configurations C 2v , the z axis passes through the sulfur atoms, and the molecules lie in the yz plane. The designation of molecules is the same as in [25]. states which produce the instability of the ground state should have the B 1u /B 1 symmetry.…”

Section: Change In the Pjte By Chemical Substitutions Puckering And mentioning

confidence: 99%

Pseudo Jahn-Teller Effect in Puckering and Planarization of Heterocyclic Compounds

Gorinchoy¹

2018

IJOC

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The goal of this brief partly review paper is to summarize the results of the works published over the last few years regarding the origin of the out-of-plane distortions (puckering) of heterocyclic compounds. In all the papers devoted to this problem, it is shown that the instability of planar configurations of heterocyclic molecules leading to symmetry breaking and distortions is induced by the pseudo Jahn-Teller effect (PJTE). Special attention in this work is paid to the mechanism of suppression and enhancement of the PJTE distortions of heterocycles by oxidation, reduction, and chemical substitutions. It is demonstrated that oxidation of 1,4-dithiine containing compounds leads to suppression of the PJTE and to restoration of their planar nuclear configurations. An example of a dibenzo[1,2]dithiine molecule is used to demonstrate the mechanism of enhancement of the PJTE by reduction. It is shown that the reduction of the neutral C 12 H 8 S 2 molecule up to the dianion (C 12 H 8 S 2) 2− enhances the PJTE, followed by the S-S bond cleavage and significant structural distortions of the system. The change of the PJTE by chemical substitutions, accompanied either by puckering or by planarization of heterocyclic compounds, is discussed using as examples 1,4-ditinine and its S-oxygenated derivatives.

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<b>DFT calculations on 1,4-dithiine and S-oxygenated derivatives</b>

Abstract: The molecular structures of 1,4-dithiine and S-oxygenated derivatives are studied using B3LYP/6-311++G** level of theory. These compounds have 8π-electrons in the ring. This led to stabilization of non-planar conformation.

Cited by 8 publications

References 15 publications

Quantum chemical estimation of the macrocyclization of 1,4-dithiine

Quantum chemical estimation of the macrocyclization of 1,4-dithiine

N,N′-Dipyridoxyl(1,8-diamino-3,6-dioxaoctane) Schiff-base: Synthesis, experimental and theoretical identification

Pseudo Jahn-Teller Effect in Puckering and Planarization of Heterocyclic Compounds

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