title: Conformationally induced electrostatic stabilization of persulfoxides: a new suggestion for inhibition of physical quenching of singlet oxygen by remote functional groups.
abstract: 1,5-Dithiacyclooctane is shown to chemically react more efficiently and to remove singlet oxygen from solution more rapidly than either thiane or 1,4-dithiane. These unusual characteristics of the 1,5-dithiacyclooctane reaction were explored using ab initio quantum chemical methods. A large number of persulfoxides, thiadioxiranes, and hydroperoxy sulfonium ylides were located and their structures analyzed. The unusual efficiency of the reaction was attributed to a conformational change that electrostatically stabilized the persulfoxide and increased the potential energy barrier for physical quenching.
authors.affiliation: Department of Chemistry, University of Wyoming, 1000 East University Avenue, Laramie WY 82071, USA. clennane@uwyo.edu
authors.forename: Edward L
authors.initials: EL
authors.lastname: Clennan
authors.forename: Sean E
authors.initials: SE
authors.lastname: Hightower
authors.forename: Alexander
authors.initials: A
authors.lastname: Greer
mesh_terms: D003198:Computer Simulation; D018360:Crystallography, X-Ray; D007700:Kinetics; D008958:Models, Molecular; D008968:Molecular Conformation; D015394:Molecular Structure; D012451:Safrole / Q000031:analogs & derivatives* / Q000138:chemical synthesis / Q000737:chemistry; D026082:Singlet Oxygen / Q000737:chemistry*; D055672:Static Electricity; D013237:Stereoisomerism
chemical_list: D026082:Singlet Oxygen; D012451:Safrole; C005746:sulfoxide