Conformationally Induced Electrostatic Stabilization of Persulfoxides:  A New Suggestion for Inhibition of Physical Quenching of Singlet Oxygen by Remote Functional Groups

• Published in: Journal of the American Chemical Society Vol. 127; no. 33; pp. 11819 - 11826
• Main Authors: Clennan, Edward L, Hightower, Sean E, Greer, Alexander
• Format: Journal Article
• Language: English
• Published: Washington, DC American Chemical Society 24.08.2005
• Subjects: Chemistry; Computer Simulation; Crystallography, X-Ray; Exact sciences and technology; General and physical chemistry; Kinetics; Models, Molecular; Molecular Conformation; Molecular Structure; Photochemistry; Physical chemistry of induced reactions (with radiations, particles and ultrasonics); Safrole - analogs & derivatives; Safrole - chemical synthesis; Safrole - chemistry; Singlet Oxygen - chemistry; Static Electricity; Stereoisomerism; Reaction path; Theoretical study; Energy barrier; Eight membered ring; Oxygen molecules; Sulfur heterocycle; Laser beam; Transition state; Density functional method; Ab initio calculations; Kinetic parameter; Rate constant; Flash photolysis; Coupled cluster method
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/ja0525509

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.