Please use this identifier to cite or link to this item: http://repositorio.unicamp.br/jspui/handle/REPOSIP/94223
Type: Artigo de periódico
Title: Spectroscopic And Theoretical Studies Of Some P-substituted α-ethylsulfonylacetophenones
Author: Olivato P.R.
Reis A.K.C.A.
Ruiz Filho R.
Zukerman-Schpector J.
Rittner R.
Dal Colle M.
Abstract: The preferred conformations of p-substituted α- ethylsulfonylacetophenones, Y-PhC(O)CH2SO2Et (Y=OMe 1, Me 2, H 3, F 4, Cl 5, Br 6, CN 7 and NO2 8) are determined by νCO IR analysis, HF/6-31G** computations (1, 3, 5, 7 and 8) and X-ray diffraction for 5 and 7. The match between IR frequencies and intensities of the carbonyl doublet components in carbon tetrachloride (first overtone) and the results of the calculations indicates that the lower frequency component corresponds to the more stable gauche (g) conformer, while the higher frequency component is related to the quasi-cis (q-c) one. The gauche conformer (g) (ca. 85%) prevails over the quasi-cis conformer (q-c) population, and the q-c/g population ratio increases on going from electron-attracting to electron-donating substituents, both in the gas phase and in solution. These trends are discussed in terms of O(SO2)δ-⋯C(CO)δ+ charge transfer (CT), O(CO)δ-⋯S(SO2)δ+ (Coulombic interaction), H[CH2(Et)]δ+⋯O(CO)δ-, H δ+(2′)(o-Ph)⋯O(CO)δ- and Hδ+(6′) (o-Ph)⋯O(SO2)δ- hydrogen bonds and electrostatic interactions, along with the πCO/σ C-S* and πCO*/σC-S orbital interactions, which stabilise the g rotamer. The stabilisation of the q-c rotamer through O(CO)δ-⋯S (SO2)δ+ (CT), Hδ+(2′) (o-Ph)⋯O(CO)δ- and H [CH2(Et)]δ+⋯O(CO)δ- hydrogen bond interactions is counterbalanced by O (CO)δ-⋯O(SO2)δ- electrostatic repulsion, which destabilises significantly this rotamer. The X-ray diffraction analyses show that 5 and 7, in the solid, adopt the cis (c′) conformation, which is stabilised through intermolecular hydrogen bonds involving the acidic α-methylene Hδ+(3A), H(3B) and m-phenyl Hδ+(5′)[m-Ph] hydrogen atoms and the Oδ-(6), Oδ-(7) sulfonyl and O δ-(1) carbonyl oxygen atoms. © 2004 Elsevier B.V. All rights reserved.
Editor: 
Rights: fechado
Identifier DOI: 10.1016/j.theochem.2004.01.032
Address: http://www.scopus.com/inward/record.url?eid=2-s2.0-2042447802&partnerID=40&md5=98b7125a13657b9caeb6487b283a5a2d
Date Issue: 2004
Appears in Collections:Unicamp - Artigos e Outros Documentos

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