Abstract
Results of a kinetic study based on 337.1-nm laser flash photolysis are presented for electron-transfer reactions with paraquat (PQ/sup 2 +/) as the oxidant for the triplets of a number of substituted benzophenones and acetophenones and the corresponding ketyl radicals. The ketyl radicals were generated from the ketone triplets by laser flash photolysis in the presence of excess of p-methoxyphenol. The electron-transfer rate constants (2 x 10/sup 8/-8 x 10/sup 9/ M/sup -1/ s/sup -1/) as well as the fractions (0.5-1.0) of the triplet quenching events that result in net reduction of PQ/sup 2 +/ correlate well with the electron-releasing nature of the substituents in the ketones. Quantitative data concerning the transient absorption spectra of substituted benzophenone triplets and diarylhydroxymenthyl radicals are also reported. 5 figures, 1 table.
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