Conformational stability, r0 structural parameters, barriers to internal rotation, vibrational spectra and ab initio calculations of c-C3H5SiH2CH3

Durig, J. R.; Panikar, Savitha S.; Guirgis, Gamil A.; Gounev, Todor K.; Ward, Rachel M.; Peebles, Rebecca A.; Peebles, Sean A.; Liberatore, Richard J.; Bell, Stephen; Wurrey, C. J.

doi:10.1016/j.molstruc.2008.12.017

Cited by 12 publications

(23 citation statements)

References 41 publications

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“…These predicted values are expected to be reasonably near the unknown experimental ones that would be obtained from the frequencies of the asymmetric torsional modes from the two conformers. Potential function results obtained for cyclopropylcyanosilane molecules are consistent with previously reported potential function values for cyclopropyl fluoro, chloro, bromo and methyl silane [4][5][6][7].…”

Section: Discussionsupporting

confidence: 90%

“…For cyclopropylsilane derivatives, conformational stability changes with respect to substitution of halogen in the silane moiety. The study of cyclopropylmethylsilane [7] showed that the gauche form was the most stable conformer with an enthalpy difference of 98 ± 13 cm À1 (1.17 ± 0.16 kJ/mol), and at ambient temperature, the amount of cis conformer was 23 ± 6%. However, these data are not enough for establishing the relationship between conformational stability and cyclopropylsilane derivatives.…”

Section: Introductionmentioning

confidence: 99%

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Microwave, r0 structural parameters, conformational stability and vibrational assignment of cyclopropylcyanosilane

et al. 2014

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Section: Discussionsupporting

confidence: 90%

Section: Introductionmentioning

confidence: 99%

Microwave, r0 structural parameters, conformational stability and vibrational assignment of cyclopropylcyanosilane

et al. 2014

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“…The gauche conformer of this molecule was the only conformer observed in the supersonic expansion of the microwave study and a barrier to rotation of the methyl group of 6.672(9) kJ mol À1 was obtained from an analysis of the internal rotation doublets [2]. The vibrational work agreed that the gauche conformer was the more stable although evidence for a cis form was also seen in the IR and Raman studies [1].…”

Section: Introductionmentioning

confidence: 60%

“…Recent studies reported IR and Raman measurements [1] and a separate analysis of the microwave spectrum and determination of the barrier to rotation [2] for cyclopropylmethylsilane (CMS). The gauche conformer of this molecule was the only conformer observed in the supersonic expansion of the microwave study and a barrier to rotation of the methyl group of 6.672(9) kJ mol À1 was obtained from an analysis of the internal rotation doublets [2].…”

Section: Introductionmentioning

confidence: 99%

Rotational spectrum of five isotopologues of cyclopropylmethylgermane: Ab initio calculations, barrier to internal rotation and nuclear quadrupole coupling constants for the 73Ge nucleus

Murray¹,

Serafin²,

Steber³

et al. 2010

Journal of Molecular Structure

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“…As a continuation of our structural and spectroscopic studies of mono-substituted cyclopropanes we were interested in methylgermylcyclopropane, c-C 3 H 5 GeH 2 CH 3 for a comparison to the conformational stability results of our recently investigated [4] methylsilylcyclopropane, c-C 3 H 5 SiH 2 CH 3 , as well as to the corresponding carbon analogue which we investigated a few years ago [5]. Also of interest were the structural parameters and the enthalpy difference between the two conformers which could possibly provide some information on the major factors contributing to the stability of the more stable form.…”

Section: Introductionmentioning

confidence: 99%

Conformational stability, r0 structural parameters, barriers to internal rotation, vibrational assignments and ab initio calculations of c-C3H5GeH2CH3

Durig

Panikar

Guirgis

et al. 2010

Journal of Molecular Structure

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a b s t r a c tThe infrared spectra (3100-40 cm À1 ) of gaseous and amorphous solid and Raman spectra (3200-20 cm À1 ) of the liquid at various temperatures for methylgermylcyclopropane, c-C 3 H 5 GeH 2 CH 3 , have been obtained. Additionally, variable temperature (À55 to À100°C) studies of the infrared spectra of the sample dissolved in xenon have been recorded. From these spectral data, two conformers have been identified with one the cis (syn) form where the methyl group is over the three-membered ring and the other the gauche form. By utilizing six conformer pairs of the vibrational bands the enthalpy difference of the sample dissolved in xenon has been determined to be 43 ± 11 cm À1 (0.51 ± 0.13 kJ mol À1 ) with the gauche form the more stable conformer. It is estimated that there is approximately 30 ± 3% of the cis form present at ambient temperature. It was not possible to achieve crystallization of the compound by annealing it, and both conformers were present at all temperatures. The Ge-H distances of 1.531 and 1.533 Å for the gauche conformer have been determined from their stretching frequencies. By utilizing the microwave rotational constants of the gauche conformer for five isotopomers ( 70 Ge, 72 Ge, 73 Ge, 74 Ge, 76 Ge) combined with the structural parameters predicted from the MP2(full)/6-311+G(d,p) calculations, the adjusted r 0 structural parameters have been obtained. The heavy atom distances (Å) are: (GeC 2 ) = 1.925(5); (C 2 C 4 ) = 1.517(3); (C 2 C 5 ) = 1.519(3); (C 4 C 5 ) = 1.502(3); (GeC 6 ) = 1.947(5) and the angles (°) are: \CGeC = 110.6(5); \GeC 2 C 4 = 120.1(5); \GeC 2 C 5 = 119.2(5). For the cis form very small differences of 0.003 and 0.001 Å from those of the gauche form are predicted for the GeC bonds whereas the other distances are predicted to be the same or differ at the most by 0.002 Å. A complete vibrational assignment is given for both the conformers. To support the vibrational assignments, normal coordinate calculations with scaled force constants from MP2(full)/6-31G(d) calculations were carried out to predict the fundamental vibrational frequencies, infrared intensities, Raman activities, depolarization values and infrared band contours. Barriers to internal rotation have been predicted. The results are discussed and compared to the corresponding properties of some similar molecules.

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Conformational stability, r0 structural parameters, barriers to internal rotation, vibrational spectra and ab initio calculations of c-C3H5SiH2CH3

Cited by 12 publications

References 41 publications

Microwave, r0 structural parameters, conformational stability and vibrational assignment of cyclopropylcyanosilane

Microwave, r0 structural parameters, conformational stability and vibrational assignment of cyclopropylcyanosilane

Rotational spectrum of five isotopologues of cyclopropylmethylgermane: Ab initio calculations, barrier to internal rotation and nuclear quadrupole coupling constants for the 73Ge nucleus

Conformational stability, r0 structural parameters, barriers to internal rotation, vibrational assignments and ab initio calculations of c-C3H5GeH2CH3

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