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Deprotonation of organic radical cations. Chemical evidence for proton transfer between 9,10-dihydroanthracence radical cations and superoxide radical anions

✍ Scribed by Ryoichi Akaba; Mitsuru Iwasaki; Tsuyoshi Matsumura; Masaki Kamata; Hiroki Itoh


Publisher
John Wiley and Sons
Year
1996
Tongue
English
Weight
264 KB
Volume
9
Category
Article
ISSN
0894-3230

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✦ Synopsis


Photoinduced electron-transfer oxygenation of 9,lO-dihydroanthracene was carried out with 2,4,6triphenylpyrylium tetrafluoroborate (TPP) and 9,lO-dicyanoanthracene (DCA) as sensitizers. The time course of the oxygenation products was studied, and the results showed that anthrone was formed as a primary product in the DCA-sensitized oxygenation whereas in the TPP-sensitized oxygenation anthracene was the primary, major product which under the reaction conditions was converted to anthrone. A mechanism involving proton transfer in the radical ion pair consisting of 9,10-dihydronathracene radical cation and superoxide radical anion, which cannot occur in the TPP-sensitized oxygenation, was proposed to rationalize the difference in the product distribution in the two sensitized oxygenation reactions.