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Rates of addition of tert-butyl and pivaloyl radicals to acrylonitrile measured by modulated ESR and μSR spectroscopy

✍ Scribed by F. Jent; H. Paul; E. Roduner; M. Heming; H. Fischer

Publisher: John Wiley and Sons
Year: 1986
Tongue: English
Weight: 439 KB
Volume: 18
Category: Article
ISSN: 0538-8066
DOI: 10.1002/kin.550181002

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✦ Synopsis

For the rate constant of addition of tert-butyl radicals to acrylonitrile at T = 300 K in solution modulated ESR spectroscopy and muon spin rotation yield lo6 M-' s-' and 2.4 x lo6 M-' s-'. The addition of pivaloyl radical to acrylonitrile proceeds with Arrhenius parameters log AIM-' s-' = 7.7 and E, = 11.5 kJ/mol. The resu!ts are discussed in terms of polar effects in radical addition rezctions.

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The Addition of tert-Butyl (Me3Ċ) and (tert-Butoxy)carbonylmethyl (Me3CO2CĊH2) radicals to alkynes in solution studied by ESR spectroscopy

✍ Herbert Rubin; Hanns Fischer 📂 Article 📅 1996 🏛 John Wiley and Sons 🌐 German ⚖ 686 KB

All arrangements and procedures for steady-state and time-resolved ESR were as described in [4]. The radicals Me,C and Me3C02CCH, were generated by photolysis of the corresponding disubstituted ketones. These undergo type-I cleavage from a short-lived triplet state followed by a fast decarbonylation