J Phys Chem A. 2015 Apr 23;119(16):3823-32. doi: 10.1021/acs.jpca.5b01531. Epub 2015 Apr 13.

Conformational Analysis and Electronic Interactions of Some 4'-Substituted-2-ethylthio-phenylacetates.

The journal of physical chemistry. A

Daniel N S Rodrigues, Lucas C Ducati, Paulo R Olivato, Maurizio Dal Colle

PMID: 25839322 DOI: 10.1021/acs.jpca.5b01531

Abstract

The conformational analysis of various 4'-substituted-2-ethylthio-phenylacetate compounds bearing the substituents NO2 (1), Cl (2), H (3), Me (4), and OMe (5) was performed using infrared (IR) spectroscopic analysis of the carbonyl stretching band (νCO) supported by B3LYP/6-31G(d,p), NBO, QTAIM, and SM5.42R calculations for compounds 1, 3, and 5. The IR spectra in n-hexane indicate the presence of three components, whose intensities decrease upon increasing frequency. In solvents with high permittivity, while the low intensity component at higher frequency disappears, the relative intensity of the component at the intermediate frequency changes with respect to the lower frequency component with differing trends for the various derivatives. It can be observed that the intensity does not vary for compounds 1 and 2, which bear an electron-withdrawing substituent at 4', while it increases in intensity for compounds 3-5. The computational results predict the presence of three gauche conformers, defined by the orientation of the C-S bond with respect to the carbonyl group, whose intensities and νCO frequencies are in agreement with the experimental results. In solvents with increasing permittivity, the SM5.42R solvation model results reproduce the experimental trend observed for the two components in the low frequency region, while it overestimates the amount of the higher frequency conformer. NBO analysis suggests that all the conformers are stabilized to the same extent in the gauche conformation via σC-S → π*CO and πCO → σ*C-S orbital interactions. The different stability can be attributed to the geometrical arrangement of the C(O)-CH2-S-CH2-CH3 moiety, which assumes a six-membered chair-like geometry in the g1 conformer, a six-membered twisted-chair-like geometry in the g2 conformer, and a seven-membered chair-like ring in the g3 conformer. Quantum theory of atoms in molecules (QTAIM) indicates that the ring geometries were formed and stabilized from short contacts between the oppositely charged carbonyl oxygen and the methylene/methyl hydrogen atoms, which interact through unusual intramolecular electrostatic hydrogen bonding that satisfies the Popelier criteria.

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