An electron spin resonance study of aminoallyl, aminopropynyl, and aminocyanomethyl radicals

David Griller, Derek C. Nonhebel, John C. Walton*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

18 Citations (Scopus)

Abstract

E.s.r. spectra have been obtained for series of N-alkyl-substituted aminoallyl and aminopropynyl radicals and for aminocyanomethyl radicals. The hyperfine splittings indicate that considerable spin density is delocalised on to the NR2 group. The amino group is a more effective acceptor of spin than alkyl-, halogen, hydroxy- or alkoxy-substituents and only slightly less effective than the vinyl substituent. The barrier to rotation about the C-N bond in aminopropynyl radicals was calculated to be 44 ± 5 kJ mol -1 from the temperature dependence of the e.s.r. line widths, and this leads to a value of 107 kJ mol-1 for the methane-based stabilisation energy of the radical. The geometries, enthalpies of formation, and stabilisation energies of the series of N-alkyl-substituted allyl and propynyl radicals were also investigated by semi-empirical SCF MO methods.

Original languageEnglish
Pages (from-to)1373-1379
Number of pages7
JournalJournal of the Chemical Society, Perkin Transactions 2
Issue number9
DOIs
Publication statusPublished - 1 Jan 1983

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