Molecular structure of divinyl sulphone as studied by electron diffraction, vibrationai spectroscopy, and semiempirical CNDO/2 molecular-orbital calculations

Hargittai, István; Rozsondai, B.; Nagel, B.; Bulcke, P.; Robinet, Germaine; Labarre, Jean

doi:10.1039/dt9780000861

Cited by 14 publications

(7 citation statements)

References 1 publication

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“…The calculated S--O distance is somewhat larger than the experimental value, a rather unusual fact at the HF level. But in this case the experimental value could probably be in error, since it is 0.007 A, shorter than those determined for (CH3) 2SO 2 [9c] and (CH2CH)2SO2 [6].…”

Section: Ab Initio Conformational Analysismentioning

confidence: 54%

“…study of Ref. 6 would then be at least controvertible, since, even within the refinement scheme (set B) more consistent with our theoretical results, a significant relative abundance of the CI form was determined, and the same conformational ratio for both the Ca and Cs conformers was obtained.…”

Section: Conformational Analysis Of Vinyl Fluoro Sulfone Vinyl Chlormentioning

confidence: 70%

“…Since no definitive conclusions about the conforo mational properties could be drawn in the E.D. studies of the related molecules vinyl chloro sulfone (CH2CHSO2C1) [5] and divinyl sulfone ((CH2CH)2SO2) [6], we felt that a theoretical conformational analysis of these molecules would be worthwhile. The results of this analysis, extended also to vinyl fluoro sulfone (CH2CHSO2F), have been included herein.…”

Section: Introductionmentioning

confidence: 99%

“…In fact, HF/6-31G** frequency calculations [10] are successful in reproducing the order proposed for the sulfonyl deformations in a vibrational analysis of divinyl sulfone [6], but fail in the case of dimethyl sulfone [11], where experimental evidences would seem to be conclusive. Since in the case of MVS, due to its low symmetry, the analysis should have been done on the basis of relative intensities and depolarization ratios of Raman bands, we thought any conclusion drawn would have been controvertible.…”

mentioning

confidence: 98%

“…The wavenumbers observed in the IR and Raman spectra of liquid MVS are collected in Table IV. The fundamental vibrations were assigned mainly on the basis of the HF/6-31G** calculated vibrational frequencies and normal modes characterization, but the assignments were tested with spectra of related molecules [6,11].…”

mentioning

confidence: 99%

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Conformational properties of methyl vinyl sulfone: Ab initio geometry optimization and vibrational analysis

Fantoni

Marañon

1996

Struct Chem

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An ab initio conformational analysis of methyl vinyl sulfone (CH2CHSO2CH3) has been carded out. Molecular geometry optimizations have been performed at the HF and MP2 levels of the theory. Relative energies of the stationary points have been determined by using different approaches, including electron correlation corrections up to the third order. The IR and Raman spectra of the liquid have been measured and a vibrational assignment is proposed. The height of the barrier to the methyl group internal rotation has been estimated. Theoretical calculations and vibrational spectra have shown that the predominant conformation of methyl vinyl sulfone has the C=C bond eclipsed with one of the S=O bonds. Similar eclipsed forms have been found in vinyl fluoro sulfone, vinyl chloro sulfone and divinyl sulfone by ab initio HF calculations.

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Section: Ab Initio Conformational Analysismentioning

confidence: 54%

Section: Conformational Analysis Of Vinyl Fluoro Sulfone Vinyl Chlormentioning

confidence: 70%

Section: Introductionmentioning

confidence: 99%

mentioning

confidence: 98%

mentioning

confidence: 99%

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Conformational properties of methyl vinyl sulfone: Ab initio geometry optimization and vibrational analysis

Fantoni

Marañon

1996

Struct Chem

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Elektronendomänen und das VSEPR‐Modell der Molekülgeometrie

Gillespie

Robinson

1996

Angewandte Chemie

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Electron Domains and the VSEPR Model of Molecular Geometry

Gillespie

Robinson

1996

Angew. Chem. Int. Ed. Engl.

220

150

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The valence shell electron pair repulsion (VSEPR) model-also known as the Gillespie-Nyholm rules-has for many years provided a useful basis for understanding and rationalizing molecular geometry, and because of its simplicity it has gained widespread acceptance as a pedagogical tool. In its original formulation the model was based on the concept that the valence shell electron pairs behave as if they repel each other and thus keep as far apart as possible. But in recent years more emphasis has been placed on the space occupied by a valence shell electron pair, called the domain of the electron pair, and on the relative sizes and shapes of these domains. This reformulated version of the model is simpler to apply, and it shows more clearly that the Pauli principle provides the physical basis of the model. Moreover, Bader and his co-workers' analysis of the electron density distribution of many covalent molecules have shown that the local concentrations of electron density (charge concentrations) in the valence shells of the atoms in a molecule have the same relative locations and sizes as have been assumed for the electron pair domains in the VSEPR model, thus providing further support for the model. This increased understanding of the model has inspired efforts to examine the electron density distribution in molecules that have long been regarded as exceptions to the VSEPR model to try to understand these exceptions better. This work has shown that it is often important to consider not only the relative locations and sizes, but also the shapes, of both bonding and lone pair domains in accounting for the details of molecular geometry. It has also been shown that a basic assumption of the VSEPR model, namely that the core of an atom underlying its valence shell is spherical and has no influence on the geometry of a molecule, is normally valid for the nonmetals but often not valid for the metals, including the transition metals. The cores of polarizable metal atoms may be nonspherical because they include nonbonding electrons or because they are distorted by the ligands, and these nonspherical cores may have an important influence on the geometry of a molecule.

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Molecular structure of divinyl sulphone as studied by electron diffraction, vibrationai spectroscopy, and semiempirical CNDO/2 molecular-orbital calculations

Cited by 14 publications

References 1 publication

Conformational properties of methyl vinyl sulfone: Ab initio geometry optimization and vibrational analysis

Conformational properties of methyl vinyl sulfone: Ab initio geometry optimization and vibrational analysis

Elektronendomänen und das VSEPR‐Modell der Molekülgeometrie

Electron Domains and the VSEPR Model of Molecular Geometry

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