An electron spin resonance study of 1-alkylthioallyl, 3-alkylthiopropynyl, and alkylthioalkyl radicals: An examination of spin delocalization by alkylthio groups

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

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

27 Citations (Scopus)

Abstract

E.s.r. spectra have been recorded for CH2CHĊHSBu t and HC≡CĊHSBut. The hyperfine splitting constants indicate that considerable spin density is delocalized onto the SBut group. This group is a more effective acceptor of spin than alkyl, hydroxy, or alkoxy substituents, and comparable with that of an ethynyl substituent. The barrier to rotation about the Cα-S bond in AdSĊH2 is greater than that about the Cα-O bond in AdOĊH2 as a consequence of greater spin delocalization onto sulphur than onto oxygen. The mechanism of reaction of t-butoxyl radicals with sulphides is discussed. The ButSĊHCH2OCH3 radical exists in an eclipsed conformation whereas ButSĊHCH 2Ph and CH3OĊHCH2Ph prefer staggered conformations.

Original languageEnglish
Pages (from-to)1817-1821
Number of pages5
JournalJournal of the Chemical Society, Perkin Transactions 2
Issue number11
Publication statusPublished - 1 Dec 1984

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