Kinetic applications of electron paramagnetic resonance spectroscopy. XIV. 1,1-Dialkylhydrazyl radicals

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DOIResolve DOI: http://doi.org/10.1021/ja00819a036
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TypeArticle
Journal titleJournal of the American Chemical Society
ISSN0002-7863
Volume96
Issue12
Pages39493954; # of pages: 6
AbstractThe self-reactions of 1,1-dialkylhydrazyl radicals at ambient temperatures have been examined by kinetic epr spectroscopy. Dimethyl-, diethyl-, and dibenzylhydrazyls decay rapidly with bimolecular kinetics. The products suggest that the initial reaction is a dimerization but that the resulting tetrazane is unstable and decomposes to amine and nitrogen. Diisopropylhydrazyl and the hydrazyl derived from 1-amino-2,2,6,6-tetramethylpiperidine decay slowly with first-order kinetics. These radicals exist in equilibrium with their dimer. Decay involves a disproportionation reaction of the free radicals with the formation of the parent hydrazine and an N-nitrene. The dialkylaminonitrenes decompose to hydrocarbons and nitrogen. Arrhenius parameters for these decays and the heats of dimerization were determined. The results are discussed both in relation to classical studies of the oxidation of 1,1-dialkylhydrazines and in relation to the decay processes for the isoelectronic alkylperoxy radicals and dialkyl nitroxides.
Publication date
LanguageEnglish
AffiliationNational Research Council Canada (NRC-CNRC)
Peer reviewedYes
NPARC number21276757
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Record identifier966d5468-fc11-4b31-aa7b-5b40f993f032
Record created2015-10-13
Record modified2016-05-09
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