Kinetic applications of electron paramagnetic resonance spectroscopy. XXIII. Cyanomethyl radicals

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DOIResolve DOI: http://doi.org/10.1021/ja00418a033
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TypeArticle
Journal titleJournal of the American Chemical Society
ISSN0002-7863
Volume98
Issue2
Pages523526; # of pages: 4
AbstractDicyanomethyl and tricyanomethyl have been prepared and examined by EPR spectroscopy. Their EPR parameters at 20° are: HĊ(CN)2, g = 2.0033, aH = 19.18, aN = 2.75, a13Cα = 29.18 G; Ċ(CN)3, g = 2.0033, aN = 2.28, a13Cα = 22.06, a13Cβ = 18.20. It is concluded, on the basis of the 13Cα couplings and from the results of INDO calculations, that both radicals are planar. The 13Cα couplings, which were measured with enriched material, increase slightly with increasing temperature because the magnitude of the out-of-plane vibrations of the Cα substituents increases. Both radicals decay with second-order kinetics, the HĊ(CN)2 radical at close to the diffusion-controlled limit (k2EPR = 1.2 × 1.2 × 109 sec-1 at 20°), but Ċ(CN)3 decays considerably more slowly.
Publication date
LanguageEnglish
AffiliationNational Research Council Canada (NRC-CNRC)
Peer reviewedYes
NPARC number21276619
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Record identifiera8b41e8d-79cc-464f-a388-241929f99062
Record created2015-10-13
Record modified2016-05-09
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