Comparison of experimental and computationally predicted sulfoxide bond dissociation enthalpies.

The accurate estimation of S-O bond dissociation enthalpies (BDE) of sulfoxides by computational chemistry methods has been a significant challenge. One of the primary causes for this challenge is the well-established requirement of including high-exponent d functions in the sulfur basis set for accurate energies. Unfortunately, even when high-exponent d functions were included in Pople-style basis sets, the relative strength of experimentally determined S-O BDE was incorrectly predicted.

Photodeoxygenation of dibenzothiophene S-oxide derivatives in aqueous media.

The use of atomic oxygen (O((3)P)) as potent oxidant in water has suffered from the lack of a facile, efficient source. The photodeoxygenation of aromatic sulfoxides to the corresponding sulfides in organic solvents has been suggested to produce O((3)P) in low quantum yields. The photolysis of 4,6-dihydroxymethyldibenzothiophene S-oxide and 2,8-dihydroxymethyldibenzothiophene S-oxide in water results in deoxygenation at significantly higher quantum yields than in organic solvents.