He(I)/He(II) ultraviolet photoelectron spectroscopic studies on organosulfur compounds with emphasis on the sulfur-oxygen interaction

István Pál Csonka, Gábor Vass, László Szepes, Dénes Szabó, István Kapovits

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Abstract

The electronic structure of compounds having the possibility of exhibiting intramolecular sulfur-oxygen non-bonded interaction of the S(II, IV or VI)···O(carbonyl or nitro) type and a hypervalent sulfur atom of the O-S-O type - i.e, R-S-Me, R-SO-Me, R-SO2-Me (R = 2-nitrophenyl; 2, 7 and 12), R-S-R, R-SO-R, R-SO2-R (R = 2-methoxycarbonylphenyl; 5, 10 and 15) and spirosulfurane (16) - have been investigated by the He(I) and He(II) ultraviolet photoelectron spectroscopic method. Reference compounds with R = phenyl or 4-nitrophenyl group (1, 3, 4, 6, 8, 9, 11, 13 and 14) were also studied for the sake of completeness and uniformity. On the basis of the photoelectron spectra and ab initio Hartree-Fock calculations, the sulfur-oxygen non-bonded interaction in compounds 2, 7, 12 and 5, 10, 15 can be attributed to electrostatic interaction. The sulfur-oxygen bond in the sulfoxides and sulfones, which is usually considered as a polarized double bond, seems to be a single bond with zwitterionic character. The photoelectron spectra of spirosulfurane (16) show no similarity to those of the symmetrical disubstituted sulfide, sulfoxide and sulfone (5, 10 and 15).

Original languageEnglish
Pages (from-to)141-159
Number of pages19
JournalJournal of Molecular Structure: THEOCHEM
Volume455
Issue number2-3
DOIs
Publication statusPublished - dec. 18 1998

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ASJC Scopus subject areas

  • Biochemistry
  • Condensed Matter Physics
  • Physical and Theoretical Chemistry

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