Journal of the American Chemical Society, Vol.121, No.18, 4364-4368, 1999
Photosensitized reduction of sulfonium salts: Evidence for nondissociative electron transfer
The photosensitized reductions of 4-cyanobenzylmethylphenyl sulfonium tetrafluoroborate (1-BF4) by 9-phenylanthracene, 2-ethyl-9,10-dimethoxyanthracene, or perylene excited singlet states gives quantitative yields of phenyl methyl sulfide. Fluorescence quenching and the quantum yields for product formation, as functions of [1-BF4], give bimolecular rate constants (0.58-1.6 x 10(10) M-1 s(-1)) for reaction of the excited sensitizers with the sulfonium salt. The limiting quantum yields, corresponding to infinite [1-BF4], are 0.65-0.77 for the three sensitizers, revealing significant inefficiencies in the photoreduction, These inefficiencies are assigned to the partitioning of a sulfuranyl radical intermediate in a two-step associative electron-transfer mechanism.