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Effect of Concentrations of Radical-ion Intermediates in the Photochemical Redox Reaction of the Diphenylmethyl Radical by Hajime Yokoi; Shin Moriizumi; Katsuya Ishiguro; Yasuhiko Sawaki is a scholarly article available to read on EtoBox.

What is Effect of Concentrations of Radical-ion Intermediates in the Photochemical Redox Reaction of the Diphenylmethyl Radical about?

Effect of concentrations of radical ion intermediates in photoinduced electron transfer (PET) reactions was examined for the redox reaction of diphenylmethyl radical. The irradiation of sym-tetraphenylacetone in the presence of aromatic donor and acceptor in MeOH± MeCN (1:9) leads to (i) the simultaneous generation of diphenylmethyl radical and a pair of radical ions, (ii) the electron transfers between them affording diphenylmethyl cation and anion, and (iii) the formation of Ph 2 CHOMe and Ph 2 CH 2 by the trapping reactions with methanol. The product ratios of Ph 2 CH 2 /Ph 2 CHOMe are shown to be dominated by the steady-state concentrations of radical ions. Thus, pulsed irradiations resulted in quite different product ratios depending on the pulse intervals. The relative rates extrapolated to in®nite, which are directly related to the intrinsic electron transfer rates with radical ions, are shown to follow the Rehm±Weller-type relationship. The importance of the persistent radical ion effect for PET reactions, just as the Ingold±Fischer persistent radical one, is discussed.

Author

Hajime Yokoi; Shin Moriizumi; Katsuya Ishiguro; Yasuhiko Sawaki

Publisher

Elsevier Science; Elsevier ; Elsevier BV (ISSN 1010-6030)

Published

1999

Language

EN