Studies of the Formation and Stability of Pentadienyl and 3-Substituted Pentadienyl Radicals

K. Brady Clark*, David Griller, Peter N. Culshaw, John C. Walton, F. P. Lossing, J. A.Martinho Simôes

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

46 Citations (Scopus)

Abstract

Pentadienyl radicals and their 3-methyl and 3-hydroxy derivatives were generated from the corresponding 1, 4-pentadienes. The rates of hydrogen abstraction were studied by laser flash photolysis, and the bisallylic C-H bond dissociation energies were determined by photoacoustic calorimetry. Pentadienyl radicals were also generated by monoenergetic electron bombardment of 3-tert-butyl-1,4-pentadiene, and the radical’s enthalpy of formation was deduced from the appearance energy of the tert-butyl cation. Evaluation of all recent data leads to recommended values of [formula omitted] (pentadienyl) = 49.8 ± 1.0 kcal mol−1 and DH°((CH2=CH)2CH) = 76.6 ± 1.0 kcal mol−1. The EPR spectra of 3-methylpentadienyl and several other radicals were also examined. The effect of substituents on the stabilization energy of pentadienyl radicals was assessed, and pentadienyl radicals were compared with other delocalized polyenyl radicals.

Original languageEnglish
Pages (from-to)5535-5539
Number of pages5
JournalThe Journal of Organic Chemistry
Volume56
Issue number19
DOIs
Publication statusPublished - 1 Sept 1991

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