title: The degree of rotation independence of conjugation of S-N bonds.
abstract: The electron delocalization in pi-electron systems is frequently described qualitatively by the concept of conjugation between formal double bonds separated by a formal single bond. In carbon compounds the optimum conjugation usually requires a rather strict, geometrical condition: the exact or near coplanarity of the participating carbon atoms. However, the geometrical conditions are much less strict for third-row atoms if the bonding involves valence-shell d orbitals. In some sulfur compounds, such as N-sulfonylsulfilimines, the conjugation is almost unaffected within large ranges of bond-rotation angles, which amounts to rotation-independent conjugation. On the basis of the indications of earlier, limited studies using only minimal basis set and no geometry optimization, in the more extensive present study Density Functional Theory B3LYP calculations using 6-31G basis set provide more reliable evidence for such flexible conjugation in some sulfur compounds and give an explanation for the experimentally observed interconversion of chiral conformers of N-sulfonylsulfilimines.
authors.affiliation: Department of Chemistry, Scientific Modeling and Simulation Laboratory (SMSL), Memorial University of Newfoundland, St. John's, NL A1B 3X7, Canada.
authors.forename: Lijie
authors.initials: L
authors.lastname: Wang
authors.forename: Paul G
authors.initials: PG
authors.lastname: Mezey