Reactions of triplet carbenes with sulfides and disulfides: ylide vs. radical formation

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DOIResolve DOI: http://doi.org/10.1021/ja00271a035
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TypeArticle
Journal titleJournal of the Americal Chemical Society
ISSN0002-7863
Volume108
Issue11
Pages30243028; # of pages: 5
AbstractThe reactions between triplet diphenylcarbene and fluorenylidene with a variety of sulphides and disulfides were investigated with use of electron paramagnetic resonance (EPR) spectroscopy, laser flash photolysis, and product studies. Diphenylcarbene reacted with these substrates by a radical-like displacement mechanism. Rate constants were ca. 10⁶ M⁻1 s⁻1, and the resulting thio-substituted diphenylmethyl radicals were identified by their EPR and optical spectra. By contrast, the analogous reactions of fluorenylidene had rate constants of 10⁸-10⁹ M⁻¹ s⁻¹ and proceeded by an ylide mechanism. Product studies were consistent with these results but were not sufficient in themselves to reveal these mechanistic differences.
Publication date
LanguageEnglish
AffiliationNational Research Council Canada
Peer reviewedYes
NRC number25529
NPARC number21275099
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Record identifiercc91d10e-5f8a-41e4-88dc-65244bfee470
Record created2015-05-07
Record modified2016-05-09
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