title: Effect of beta-alkylthioethyl substitution in 1,3-dithianes: quasianchimeric assistance in photoinduced electron transfer?
abstract: Nanosecond laser flash photolysis (LFP) experiments show that the rates of ET quenching of triplet benzophenone by 2-alkyldithianes significantly decrease with bulkier substitution. Introduction of sulfur at the beta-position of the flexible alkyl chain reverses this trend, whereas such substitution at the alpha-position has negligible effect. This is rationalized in terms of the three electron two center bonds, favorable due to the formation of five-membered cyclic radical cations in the case of beta-substitution, which is supported by DFT computations.
authors.affiliation: Department of Chemistry and Biochemistry, University of Denver, Denver, Colorado 80208, USA.
authors.forename: Roman V
authors.initials: RV
authors.lastname: Valiulin
authors.forename: Andrei G
authors.initials: AG
authors.lastname: Kutateladze