title: Mesolysis Mechanisms of Aromatic Thioether Radical Anions Studied by Pulse Radiolysis and DFT Calculations.
abstract: The mesolysis mechanisms for eight aromatic thioether radical anions (ArCH2SAr'(•-)) generated during radiolysis in 2-methyltetrahydrofuran were studied by spectroscopic measurements and DFT calculation. Seven of ArCH2SAr'(•-) underwent mesolysis via dissociation of the σ-bond between the benzylic carbon and sulfur atoms, forming the corresponding radical and anion with the stepwise mechanism or concerted mechanism. Conversely, no mesolysis in the benzyl β-naphthyl sulfide radical anion was found. From the Arrhenius analysis of the mesolysis with the stepwise mechanism, apparent activation energies (ΔEexp) were determined and compared with those (ΔEcal) estimated by the DFT calculations. Two types of C-S bond dissociation are possible to give the C radical and S anion (ArCH2(•)/Ar'S(-)) and the C anion and S radical (ArCH2(-)/Ar'S(•)). The dissociation energies (BDE(ArCH2(•)/Ar'S(-)) and BDE(ArCH2(-)/Ar'S(•))) were estimated by the DFT calculations, and BDE(ArCH2(•)/Ar'S(-)) were found to be smaller than BDE(ArCH2(-)/Ar'S(•)). The formation of ArCH2(•)/Ar'S(-) was observed on the mesolysis of five ArCH2SAr'(•-), while one ArCH2SAr'(•-) provided ArCH2(-)/Ar'S(•). Chemical properties governing the mesolysis mechanisms of ArCH2SAr'(•-) are discussed.
authors.affiliation: †Division of Molecular Science, Graduate School of Science and Engineering, Gunma University, Kiryu, Gunma 376-8515, Japan.
authors.forename: Minoru
authors.initials: M
authors.lastname: Yamaji
authors.affiliation: ‡The Institute of Scientific and Industrial Research (SANKEN), Osaka University, Ibaraki, Osaka 567-0047, Japan.
authors.forename: Sachiko
authors.initials: S
authors.lastname: Tojo
authors.affiliation: ‡The Institute of Scientific and Industrial Research (SANKEN), Osaka University, Ibaraki, Osaka 567-0047, Japan.
authors.forename: Mamoru
authors.initials: M
authors.lastname: Fujitsuka
authors.affiliation: ‡The Institute of Scientific and Industrial Research (SANKEN), Osaka University, Ibaraki, Osaka 567-0047, Japan.
authors.forename: Akira
authors.initials: A
authors.lastname: Sugimoto
authors.affiliation: ‡The Institute of Scientific and Industrial Research (SANKEN), Osaka University, Ibaraki, Osaka 567-0047, Japan.
authors.forename: Tetsuro
authors.initials: T
authors.lastname: Majima