Kinetic applications of electron paramagnetic resonance spectroscopy. XVIII. Persistent vinyl, alkyl, and allyl radicals

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DOIResolve DOI: http://doi.org/10.1021/ja00848a021
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TypeArticle
Journal titleJournal of the American Chemical Society
ISSN0002-7863
Volume97
Issue15
Pages42694275; # of pages: 7
AbstractFive 1,2-disubstituted, R 1C=CHMR n. and fifteen trisubstituted, R 1C=C(R 2)MR n vinyl radicals were prepared at room temperature in solution by addition of a variety of radicals, ·MR n, to a number of mono- and disubstituted acetylenes. For steric reasons many of these vinyls are relatively long lived. Some decay with first-order and some with second-order kinetics. Their EPR spectra are discussed in terms of "linear" and "bent" structures. It is concluded that only Me 3SiĊ=C(SiMe 3) 2 is truly "linear". In certain systems prolonged reaction leads to the formation of various highly persistent alkyl radicals. The EPR spectra of these alkyls and some of their decay kinetics are also reported. Ten "perpendicular" allyls, (Me 3C) 2ĊC(MR n)=CR 1R 2, of great persistence were prepared by addition of ·MR n to two di-tert-butylvinylidenecy-clopropanes. The EPR spectra of these allyls are compared with those of the corresponding (Me 3C) 2ĊCH 2MR n radicals, since the two types of radicals have similar structures. It is pointed out that in gaining persistence the allyl radicals lose their stabilization.
Publication date
LanguageEnglish
AffiliationNational Research Council Canada (NRC-CNRC)
Peer reviewedYes
NPARC number21276621
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Record identifierd8704645-d938-4ce2-aeab-c8f990233390
Record created2015-10-13
Record modified2016-05-09
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