Absolute rate constants for the addition of triethylsilyl radicals to various unsaturated compounds

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DOIResolve DOI: http://doi.org/10.1021/ja00348a055
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TypeArticle
Journal titleJournal of the American Chemical Society
ISSN0002-7863
Volume105
Issue10
Pages32923296; # of pages: 5
AbstractThe absolute rate constants for the reaction of Et3Si· radicals with a large number of unsaturated compounds have been measured by laser flash photolysis techniques. The reactivities of C=C double bonds have a wide range, e.g., the rate constants at ca. 300 K are 1.1 × 109, 2.2 × 108, 1.0 × 107, 3.7 × 106, and 9.4 × 105 M-1 s-1 for acrylonitrile, styrene, tetrachloroethylene, 1-hexene, and cyclohexene, respectively. The range of reactivities for addition to aromatic and heteroaromatic compounds is rather small, the rate constants at ca. 300 K varying from 4.6 × 105 M-1 s-1 for benzene to 5.0 × 106 M-1 s-1 for thiophene and α-methylnaphthalene. Acetylenes are slightly less reactive than structurally analogous 1-olefins. For the other types of multiple bonds examined, reactivities decreased in the order isocyanide > nitrone > nitro > isocyanate > nitrile. Arrhenius parameters were determined for a few olefins including ethylene, for which an EPR spectroscopic competition procedure was required. For styrene, log (A/(M-1 s-1)) = 9.35 ± 0.23 and Ea = 1.37 ± 0.29 kcal/mol; for ethylene, log (A/(M-1 s-1)) = 8.40 ± 0.60 and Ea = 1.40 ± 0.80 kcal/mol. © 1983 American Chemical Society.
Publication date
LanguageEnglish
AffiliationNational Research Council Canada (NRC-CNRC)
Peer reviewedYes
NPARC number21276659
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Record identifier2aee3d29-475a-4736-9486-58c24fbc0319
Record created2015-10-13
Record modified2016-05-09
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