The structure of amidyl radicals. Evidence for the π-electronic ground state and for twist about the acyl-nitrogen bond by electron paramagnetic resonance spectroscopy

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DOIResolve DOI: http://doi.org/10.1021/ja00393a021
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TypeArticle
Journal titleJournal of the American Chemical Society
ISSN0002-7863
Volume103
Issue3
Pages624628; # of pages: 5
AbstractThe EPR spectroscopic parameters for a number of acyclic N-alkylcarboxamidyls, RṄC(O)Ŕ, have been measured over a wide range of temperatures. The results can only be interpreted in terms of a π-electronic configuration in which the unpaired electron resides mainly in an N 2p orbital perpendicular to the RNC plane. Measurements of the 13C hyperfine splittings (hfs) for some RṄC(O)13CH3 demonstrate that the O and 13C atoms lie in or near the RNC plane except when R is tert-butyl, in which case steric forces twist these atoms out of this plane by 20° or more. There is less conjugative delocalization of the unpaired electron from N to O in the Me3CṄC(O)R′ radicals because they are twisted and hence these radicals have a larger N hfs and a smaller g value than amidyls which have R = primary or secondary alkyl. The first cyclic amidyl, 5,5-dimethyl-2-oxopyrrolidin-1-yl, has been detected. This radical has a smaller N hfs (11.2 G) and a higher g value (2.0063) than the acyclic radicals. © 1981 American Chemical Society.
Publication date
LanguageEnglish
AffiliationNational Research Council Canada (NRC-CNRC)
Peer reviewedYes
NPARC number21276491
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Record identifiered34c67d-4dc7-4d7f-9a08-2054619db7d9
Record created2015-10-13
Record modified2016-05-09
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