<i>Ab Initio</i> Conformational Analysis of 1,4-Dioxane

Chapman, Darren M.; Hester, R. E.

doi:10.1021/jp962932o

Cited by 71 publications

(48 citation statements)

References 19 publications

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“…[32][33][34][35] On the one hand, THF has a relatively flat 5-member ring that possesses puckering out of the planar configuration, with the flatness of this ring structure producing a number of conformations that lie close in energy. Further, low potential energy barriers for pseudo-rotation between its conformations enable essentially free rotation between minima.…”

Section: Structure and Spectroscopy Of Cyclic Ethersmentioning

confidence: 99%

“…32,33 On the other hand, it has been well established that both THP and 1,4-dioxane exist in their lowest energy chair conformations. 34,35 These, respectively, have C s and C 2h symmetries. In the interest of making fruitful comparisons regarding the behavior of these three cyclic ethers, we consider THF through an average over the C 2 to C s conformations; with experimental results having revealed that both conformations exist in near equal proportions at roomlike temperatures.…”

Section: Structure and Spectroscopy Of Cyclic Ethersmentioning

confidence: 99%

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A dynamical (e,2e) investigation of the structurally related cyclic ethers tetrahydrofuran, tetrahydropyran, and 1,4-dioxane

Builth-Williams¹,

Bellm²,

Chiari³

et al. 2013

The Journal of Chemical Physics

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Triple differential cross section measurements for the electron-impact ionization of the highest occupied molecular orbitals of tetrahydropyran and 1,4-dioxane are presented. For each molecule, experimental measurements were performed using the (e,2e) technique in asymmetric coplanar kinematics with an incident electron energy of 250 eV and an ejected electron energy of 20 eV. With the scattered electrons being detected at −5°, the angular distributions of the ejected electrons in the binary and recoil regions were observed. These measurements are compared with calculations performed within the molecular 3-body distorted wave model. Here, reasonable agreement was observed between the theoretical model and the experimental measurements. These measurements are compared with results from a recent study on tetrahydrofuran [D. B. Jones, J. D. Builth-Williams, S. M. Bellm, L. Chiari, C. G. Ning, H. Chaluvadi, B. Lohmann, O. Ingolfsson, D. Madison, and M. J. Brunger, Chem. Phys. Lett. 572, 32 (2013)] in order to evaluate the influence of structure on the dynamics of the ionization process across this series of cyclic ethers.

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Section: Structure and Spectroscopy Of Cyclic Ethersmentioning

confidence: 99%

Section: Structure and Spectroscopy Of Cyclic Ethersmentioning

confidence: 99%

A dynamical (e,2e) investigation of the structurally related cyclic ethers tetrahydrofuran, tetrahydropyran, and 1,4-dioxane

Builth-Williams¹,

Bellm²,

Chiari³

et al. 2013

The Journal of Chemical Physics

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“…20 -22 An interesting feature of the Raman spectra of liquid dioxane are very weak bands at 634, 555, 523 and 274 cm 1 . According to an ab initio study, 23 there exist several other conformations of dioxane in addition to the most stable one, the chair. In order of increasing energy of formation, the two closest in energy to the chair structure are 2,5 twist boat, (symmetry C 2 ), and 1,4 twist boat (symmetry D 2 ), both 31.2 kJ mol 1 higher in energy.…”

Section: Normal Coordinate Analysismentioning

confidence: 99%

Spectroscopic arguments for a new crystal phase of glycolaldehyde

Mohaček-Grošev

2005

J Raman Spectroscopy

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In an attempt to elucidate the nature of glycolaldehyde dimer solid phases further, low-temperature Raman spectroscopy was employed and phonon spectra were recorded in the temperature in range 10-300 K. It seems probable that the a phase of glycolaldehyde dimer belongs to the P2 1 /n space group with Z = 2, the same crystal class in which 1,4-dioxane and DL-glyceraldehyde crystallize. Studying the temperature dependence of the low-wavenumber Raman bands of glycolaldehyde dimer a phase, one observes an increase in the number of phonons from six to 13 when the sample is cooled below 80 K. We suggest that a phase transformation into a new phase g takes place, with the number of molecules per unit cell probably equal to Z = 4. Normal coordinate analysis was performed for glycolaldehyde dimer with two equatorial and with two axial hydroxyl groups, in order to predict the number of internal modes falling in the phonon region. If there were any centrosymmetric dimers with two axial hydroxyl groups present, than a band around 150 cm −1 would have been expected in the Raman spectrum, which was not observed. This is by far the strongest argument in favour of the hypothesis that the a phase consists of dimers with two equatorially placed hydroxyl groups.

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“…[1][2][3][4][5][6][7][8][9][10][11][12][13][14][15] Although the conformational analysis of cyclohexane and substituted cyclohexanes have been extensively studied, [5][6][7][8][9][10]16,17 comparatively few computational studies have been reported on the conformers and ring reversal mechanisms of unsubstituted diheterocyclohexanes. [11][12][13][14] There are computational studies on stereoelectronic hyperconjugative interactions in the chair conformers of diheterocyclohexanes, 9 -14,17-25 but no reports concerning the various other conformers and the ring interconversion mechanisms of 1,4-dithiacyclohexane [1,4-dithiane, 1; eqs. (1), (2) and (3)].…”

Section: Introductionmentioning

confidence: 99%

A computational study of conformational interconversions in 1,4‐dithiacyclohexane (1,4‐dithiane)

Freeman

Derek

2003

J Comput Chem

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Ab initio molecular orbital theory with the 6-31G(d), 6-31G(d,p), 6-31+G(d), 6-31+G(d,p), 6-31+G(2d,p), 6-311G(d), 6-311G(d,p), and 6-311+G(2d,p) basis sets and density functional theory (BLYP, B3LYP, B3P86, B3PW91) have been used to locate transition states involved in the conformational interconversions of 1,4-dithiacyclohexane (1,4-dithiane) and to calculate the geometry optimized structures, relative energies, enthalpies, entropies, and free energies of the chair and twist conformers. In the chair and 1,4-twist conformers the C-Hax and C-Heq bond lengths are equal at each carbon, which suggest an absence of stereoelectronic hyperconjugative interactions involving carbon-hydrogen bonds. The 1,4-boat transition state structure was 9.53 to 10.5 kcal/mol higher in energy than the chair conformer and 4.75 to 5.82 kcal/mol higher in energy than the 1,4-twist conformer. Intrinsic reaction coordinate (IRC) calculations showed that the 1,4-boat transition state structure was the energy maximum in the interconversion of the enantiomers of the 1,4-twist conformer. The energy difference between the chair conformer and the 1,4-twist conformer was 4.85 kcal/mol and the chair-1,4-twist free energy difference (deltaG degrees (c-t)) was 4.93 kcal/mol at 298.15 K. Intrinsic reaction coordinate (IRC) calculations connected the transition state between the chair conformer and the 1,4-twist conformer. This transition state is 11.7 kcal/mol higher in energy than the chair conformer. The effects of basis sets on the 1,4-dithiane calculations and the relative energies of saturated and unsaturated six-membered dithianes and dioxanes are also discussed.

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Ab Initio Conformational Analysis of 1,4-Dioxane

Cited by 71 publications

References 19 publications

A dynamical (e,2e) investigation of the structurally related cyclic ethers tetrahydrofuran, tetrahydropyran, and 1,4-dioxane

A dynamical (e,2e) investigation of the structurally related cyclic ethers tetrahydrofuran, tetrahydropyran, and 1,4-dioxane

Spectroscopic arguments for a new crystal phase of glycolaldehyde

A computational study of conformational interconversions in 1,4‐dithiacyclohexane (1,4‐dithiane)

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