Electron delocalisation and stabilisation in heptatrienyl and polyenyl radicals

Lain G. Green, John C. Walton*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

8 Citations (Scopus)

Abstract

Heptatrienyl radicals were generated by hydrogen abstraction from hepta-1,3,6-triene with t-butoxyl radicals and observed by e.s.r. spectroscopy. The hyperfine splittings of heptatrienyl and other polyenyl radicals indicate that spin density is not uniformly distributed along the chain but more concentrated around the central region of the structure. Semi-empirical SCF MO calculations agree with this result and also show that most radical character is associated with the central region. The stabilisation energies (SE) of polyenyl radicals increase with chain length and are related to the hydrogen hyperfine splittings as in equation (i) where ∂(H1) is the average of the anti- and syn-hydrogen hyperfine splittings (G) of SEESA/kJ mol 1 =375 ±4 - (272 ±10)log10[a(H 1)/G] (i) the terminal methylene groups.

Original languageEnglish
Pages (from-to)1253-1257
Number of pages5
JournalJournal of the Chemical Society, Perkin Transactions 2
Issue number7
Publication statusPublished - 1 Dec 1984

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