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Type: Artigo de periódico
Title: Effect of Sulfur Oxidation on the Transmission Mechanism of (4)J(HH) NMR Coupling Constants in 1,3-Dithiane
Author: Gauze, GF
Basso, EA
Contreras, RH
Tormena, CF
Abstract: Long-range (4)J(HH) couplings in 1,3-dithiane derivatives are rationalized in terms of the effects of hyperconjugative interactions involving the S=O group. Theoretical and experimental studies of (4)J(HH), couplings were carried out in 1,3-dithiane-1-oxide (2), cis-1,3-dithiane-1,3-dioxide (3), 1,3-dithiane-1,1,3-trioxide (4), and 1,3-dithiane-1,1,3,3-tetraoxide (5) compounds. Hyperconjugative interactions were studied with the natural bond orbital, NBO, method. Hyperconjugative interactions involving the LPO, oxygen lone pair and sigma*(C2-S1) and sigma*(S1-C6) antibonding orbitals yield an increase of (4)J(Hcq - Hcq) couplings. Long-range (4)J(Ha-Hax), couplings were also observed between hydrogen atoms in axial orientation, which are rationalized as originating in hyperconjugative interactions involving the bonding sigma(C6-Hax) and antibonding sigma*(S=O) orbitals. The symmetry for orbital interactions is possible only when the S=O group is in the axial orientation.
Country: EUA
Editor: Amer Chemical Soc
Citation: Journal Of Physical Chemistry A. Amer Chemical Soc, v. 113, n. 11, n. 2647, n. 2651, 2009.
Rights: fechado
Identifier DOI: 10.1021/jp810981z
Date Issue: 2009
Appears in Collections:Unicamp - Artigos e Outros Documentos

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