Behavior of alkyl radical pairs in urea channels

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DOIResolve DOI: http://doi.org/10.1021/j100341a094
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TypeArticle
Journal titleThe Journal of Physical Chemistry
ISSN0022-3654
Volume93
Issue4
Pages16661670; # of pages: 5
AbstractPhotolysis of single crystals of urea/diacyl peroxide complexes at 10 K gave pairs of alkyl radicals that were separated by two molecules of carbon dioxide. At elevated temperatures the spectra became well-resolved as rotation of the radical centers became fast on the EPR time scale. The maximum resolution of the EPR hyperfine couplings was achieved when the separation between the radicals was greatest. The temperature for the onset of rapid rotation was markedly dependent on the length of the diacyl peroxide. Two radical rearrangements in the urea channels were studied: the cyclopropylmethyl ring opening and the 5-hexenyl radical cyclization. The former was virtually unaffected by the presence of the urea host while the cyclization of the 5-hexenyl radical showed a marked matrix effect.
Publication date
LanguageEnglish
AffiliationNational Research Council Canada; NRC Institute for Chemical Process and Environmental Technology
Peer reviewedNo
Identifier10294326
NPARC number12338592
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Record identifiercd55f102-ac3a-446a-96b8-b13cd79bff5f
Record created2009-09-10
Record modified2016-05-09
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