title: Interactions of arenes and thioethers resulting in facilitated oxidation.
abstract: Synthesis of 6-endo and 6-exomethylthio-2-endoarylbicyclo[2.2.1]heptanes was accomplished stereoselectively. The ionization energies, determined by photoelectron spectroscopy, and electrochemical oxidation potentials, determined by cyclic voltammetry, were lower for the 6-endomethylthio compounds than for their 6-exomethylthio analogues. Calculations supported the notion that facilitation of electron transfer in the 6-endomethylthio compounds results from through-space S...pi interaction.
authors.affiliation: Department of Chemistry, The University of Arizona, Tucson, Arizona 85721, USA.
authors.forename: Woo Jin
authors.initials: WJ
authors.lastname: Chung
authors.forename: Malika
authors.initials: M
authors.lastname: Ammam
authors.forename: Nadine E
authors.initials: NE
authors.lastname: Gruhn
authors.forename: Gary S
authors.initials: GS
authors.lastname: Nichol
authors.forename: Waheguru P
authors.initials: WP
authors.lastname: Singh
authors.forename: George S
authors.initials: GS
authors.lastname: Wilson
authors.forename: Richard S
authors.initials: RS
authors.lastname: Glass
mesh_terms: D004563:Electrochemistry; D047028:Macrocyclic Compounds / Q000737:chemistry*; D008958:Models, Molecular; D008968:Molecular Conformation; D010084:Oxidation-Reduction; D013440:Sulfides / Q000737:chemistry*
chemical_list: D047028:Macrocyclic Compounds; D013440:Sulfides