Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Photolytic Generation and the Subsequent Dimerization of 4-Alkyl-1-methylpyridinyl Radicals in Solution as Studied by Steady-state and Kinetic ESR Spectroscopy
Kimio AkiyamaToru IshiiShozo Tero-KubotaYusaku Ikegami
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1985 Volume 58 Issue 12 Pages 3535-3539

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Abstract

1-Methylpyridinyl and 4-alkyl-1-methylpyridinyl (alkyl=methyl, ethyl, isopropyl, and t-butyl) radicals were generated photolytically from their dimers in solution. Hyperfine splitting constants for these radicals were assigned and the temperature dependence was discussed. Absolute dimerization rates of these radicals in the range of −50–−100 °C were determined by analyzing the ESR signal decay during the dark period. A nearly constant activation energy of dimerization was observed for five radicals, while the frequency factor decreased with the bulkiness of 4-substituent, which are discussed in terms of the steric hindrance for the dimerization.

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