Vibrational spectra and rotational isomerism in acrylyl fluoride

Carlson, G.L.; Fateley, William G.; Witkowski, R.E.

doi:10.1021/ja01001a010

Cited by 25 publications

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“…While propenal exists almost exclusively as the s-trans form in the gas-phase (at 25OC), the propenoyl halides exist as mixtures of two isomers, s-trans and s-cis. By studying the temperature-dependent ir (7,8) and nrnr (9) spectra, it has been concluded that the major form is s-trans. Of the two SCF-MO programs available to us, CND0/2 and HAM/3, the latter predicts ionization energies in better agreement with experiment.…”

Section: Resultsmentioning

confidence: 99%

The He(I) photoelectron spectra of the propenoyl halides

Klapstein¹,

O’Brien²

1987

Can. J. Chem.

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The He(1) photoelectron spectra of propenal and the propenoyl halides, CH2=CHCOX, X = H, F, C1, Br, were measured and interpreted with the aid of semi-empirical MO calculations, comparison with results for structurally related species, and a sum-rule for the out-of-plane orbital energies. Information concerning the identities and relative energies of the higher occupied molecular orbitals of the neutral molecules could be deduced from the spectra.DIETER KLAPSTEIN et ROBERT T. O'BRIEN. Can. J. Chem. 65, 683 (1987).On a mesurC les spectres photoClectroniques He(1) du proknal et des halogknures de propknoyles, CH2=CHCOX dans lesquels X = H, F, C1 et Br, et on les interprkte I'aide de calculs d'OM semi-empiriques, de comparaisons avec des rCsultats obtenus avec des espkces qui leur sont apparenties par la structure et d'une rkgle des sommes pour les Cnergies des orbitales hors-plan. L'information relative aux identitCs et aux Cnergies relatives des orbitales molCculaires hautes occupCes des molCcules neutres peut Etre dCduite des spectres.[Traduit par la revue]

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Section: Resultsmentioning

confidence: 99%

The He(I) photoelectron spectra of the propenoyl halides

Klapstein¹,

O’Brien²

1987

Can. J. Chem.

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Raman and infrared spectra, conformational stability, barriers to internal rotation, ab initio calculations and vibrational assignment for vinyl fluoroformate

Durig

Lin

Veken³

1992

J Raman Spectroscopy

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The Raman spectra (3200-10 cm-') and infrared spectra (3500-50 cm-') of vinyl fluoroformate, H,C==CHOC(O)F, were recorded for both the gas and solid. Additionally, tbe Raman spectrum of the liquid was recorded and depolarization ratios were obtained. These data have been interpreted on tbe basis that the only stable conformation present at ambient temperature is the t r a s -t r a s , where the first f r a s refers to the vinyl moiety relative to the O-CFO bond and tbe second trans to the C-F bond relative to the = C -O bond. Anharmonic rigid asymmetric top calcolations were used to predict the C -0 and C=C stretch infrared vapor-phase contours for tbe trans-irons and the ck-truns conformers. For both conformers, the predicted C=O stretch contour agrees with the experimentally o k r v e d contour. For the C-C stretch, only the contour predicted for tbe t r a s -t r w conformer reproduces the experimental contour. From the far-infrared spectrum of the vapor obtained at a resolution of 0.1 cm-', tbe methoxy and &vhyl torsional fundamentals have been observed at 153 and 63 cm-', respectively. The structure, barrier to internal rotation and vibrational frequencies were also determined from ub iktk HartreeFock gradient calculations using both the 3-2lG and &31G* basis sets. These results are compared with those obtained experimentally a d to similar quantities for some related molecules.

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Résonance Magnétique Nucléaire en phase nématique. Exploration de la barrière d'empêchement à la libre rotation pour le fluorure d'acroyle et l'acroléine

et al. 1974

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Abstract-The NMR spectrum of acrolein and acroyl fluoride (CH,=CH-COX with X=H and F) oriented in a nematic phase has been measured and information about conformational equilibrium s-cis s-trans has been obtained. The barrier to internal rotation of the COX group has been studied with various hypotheses. Good agreement between experimental and calculated spectra has been obtained using the potential equation V(+) = &Vn(Icos n9)/2, with V, = -200 cal mol-l, V, = 1500 cal mol-l and V , -7 400 cal mo1-l for the fluorine compound, and VJ = 1200 cal mol I , Y2 = 3000 cal mol-l and V , = 2000 cal mol-J for acrolein; this last compound is found to be mostly in the s-trans conformation.Resume-Les spectres RMN de l'acroleine et du fluorure d'acroyle (CH,=CH-COX avec X = H et F) orient& dans une phase nematique ont tt6 interpret& et des informations sur l'equilibre conformationnel s-cis s-trans ont 6te obtenues. La barriere s'opposant a la libre rotation du groupement COX a Bt B Btudiee a I'aide de differentes hypoth6ses. Un bon accord a BtB obtenu entre Ies spectres experimentaux et les spectres calcules en utilisant une fonction potentiel V(+) = C,V,(1 -cos 4 ) / 2 avec Vl = -200 cal mol-l, V , = 1500 cal mol-J et V , = 400 cal mol-l pour le compose fluore; et Vl = 1200 cal mol-l, V, = 3000 cal mol-J et V , = 2000 cal mol-l pour l'acrolkine; ce dernier compose existe presque exclusivement sous la forme s-trans.

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Vibrational spectra and rotational isomerism in acrylyl fluoride

Cited by 25 publications

References 0 publications

The He(I) photoelectron spectra of the propenoyl halides

The He(I) photoelectron spectra of the propenoyl halides

Raman and infrared spectra, conformational stability, barriers to internal rotation, ab initio calculations and vibrational assignment for vinyl fluoroformate

Résonance Magnétique Nucléaire en phase nématique. Exploration de la barrière d'empêchement à la libre rotation pour le fluorure d'acroyle et l'acroléine

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