Abstract
The anti- and syn-conformers of thiophene-2-carbonyl fluoride (A) and selenophene-2-carbonyl fluoride (B) have been studied in the gas phase. The transition states have also been obtained for the interconversion of the anti- and syn-conformers. The methods used are MP2 and DFT/B3LYP and the basis sets used for all atoms are 6-311++G(d,p). The optimized geometries, dipole moments, moment of inertia, energies, energy differences and rotational barriers are reported. This study has been extended to include solvent effect. Some of the vibrational frequencies of the conformers are reported with appropriate assignments. The results indicate that in the gas phase the syn conformer is more stable and the CCSD(T)//MP2 energy differences are 2.97 kJ/mol (A) and 3.02 kJ/mol (B) and barriers of rotation are 38.50 kJ/mol (A) and 36.89 kJ/mol (B). The structures and vibrational frequencies of (A) and (B) are not much affected by the solvents but the more polar conformer gets more stabilized. The major effect of the solvents is that energy difference decreases but rotational barrier increases. The peculiar characteristic of fluorine affecting conformational preference is not observed.
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Abdallah, H.H., Ramasami, P. (2009). First Principle Study of the Anti– and Syn–Conformers of Thiophene–2–Carbonyl Fluoride and Selenophene–2–Carbonyl Fluoride in the Gas and Solution Phases. In: Allen, G., Nabrzyski, J., Seidel, E., van Albada, G.D., Dongarra, J., Sloot, P.M.A. (eds) Computational Science – ICCS 2009. ICCS 2009. Lecture Notes in Computer Science, vol 5545. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-01973-9_13
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DOI: https://doi.org/10.1007/978-3-642-01973-9_13
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