Ab Initio Molecular Orbital Studies of the Rotational Barriers and the 33S and 13C Chemical Shieldings for Dimethyl Disulfide

Ding Jiao, Michael Barfield, Jaime E. Combariza, Victor J. Hruby

Research output: Contribution to journalArticle

53 Scopus citations

Abstract

A series of ab initio molecular orbital calculations were carried out for dimethyl disulfide as a model for the disulfide bridges in proteins and peptides. The potential energy profile for rotation around the S-S bond was obtained at the HF/6-31G* level with full geometry optimization. Cis- and trans-barrier heights were estimated to be 11.40 and 6.27 kcal/mol, respectively, on the basis of fourth-order Moller-Plesset perturbation theory and 6-311G** basis sets. Calculations of the torsion angle dependence of the isotropic 33S and 13C NMR shieldings were based on the method of individual gauge for localized orbitals (iglo). These are of interest for NMR studies of the disulfide bond in peptides and proteins. The minimum in the plot of 13C shielding as a function of torsion angle occurs for a C1-S1-S2-C2 angle close to 110°, which is an optimum arrangement for lone pair back-bonding. An analysis of the paramagnetic bond contributions to the 13C shielding at C1, for example, shows that the conformational dependence is dominated by the paramagnetic contributions to the C1-H1 bond, which points away from a lone pair on S2.

Original languageEnglish (US)
Pages (from-to)3639-3643
Number of pages5
JournalJournal of the American Chemical Society
Volume114
Issue number10
DOIs
StatePublished - May 1 1992

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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