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(Reference retrieved automatically from Web of Science through information on FAPESP grant and its corresponding number as mentioned in the publication by the authors.)

Effect of Sulfur Oxidation on the Transmission Mechanism of (4)J(HH) NMR Coupling Constants in 1,3-Dithiane

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Author(s):
Gauze, Gisele F. [1] ; Basso, Ernani A. [1] ; Contreras, Ruben H. [2, 3] ; Tormena, Claudio F. [4]
Total Authors: 4
Affiliation:
[1] Univ Estadual Maringa, Dept Quim, BR-87020900 Maringa, Parana - Brazil
[2] Consejo Nacl Invest Cient & Tecn, RA-1033 Buenos Aires, DF - Argentina
[3] Univ Buenos Aires, Dept Phys, FCEyN, Buenos Aires, DF - Argentina
[4] Univ Estadual Campinas, Inst Chem, Dept Organ Chem, BR-13084971 Campinas, SP - Brazil
Total Affiliations: 4
Document type: Journal article
Source: Journal of Physical Chemistry A; v. 113, n. 11, p. 2647-2651, MAR 19 2009.
Web of Science Citations: 11
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 LP(O), 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. (AU)

FAPESP's process: 05/59649-0 - Conformational equilibria studies by nuclear magnetic resonance spectroscopy, infrared spectroscopy and theoretical calculations
Grantee:Roberto Rittner Neto
Support Opportunities: Research Projects - Thematic Grants