An electron paramagnetic resonance study of free-radical additions to trithiocarbonates and of the formation and destruction of tetrathiafulvalene by free-radical processes

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DOIResolve DOI: http://doi.org/10.1021/ja00480a034
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TypeArticle
Journal titleJournal of the American Chemical Society
ISSN0002-7863
Volume100
Issue12
Pages38683873; # of pages: 6
AbstractTris(organothiyl)methyl radicals, RnMSC(SR )2, have been generated by the addition of a variety of transient RnM- radicals to the thione sulfur of three trithiocarbonates (dimethyl trithiocarbonate (2), 1,3-dithiolane-2-thione (3), and 1,3-dithiole-2-thione (4)) and their EPR parameters have been measured. All adducts to 3 and 4 adopt a conformation in which the RnM group and the semioccupied orbital at Cα are eclipsed, but the adducts to 2 adopt noneclipsed conformations. This behavior is attributed to differences in the extent of conjugative electron delocalization to the p-type lone pair of the sulfur which bears the RnM group. Tetrathiafulvalene (6) is formed by reaction of R3Sn· radicals with 4 (cf. ref 17). Its yield passes through a maximum because the R3Sn· can attack 6 at sulfur via an SH2 process. This produces acetylene and persistent 1-thiaallyl radicals, R3SnSC̄(S̄.)C̄(SCH)2, which exist in equilibrium with their diamagnetic dimers at ambient temperatures. © 1978 American Chemical Society.
Publication date
LanguageEnglish
AffiliationNational Research Council Canada (NRC-CNRC)
Peer reviewedYes
NPARC number21276629
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Record identifiercf74c31e-48ee-4311-9a16-3280228f54f7
Record created2015-10-13
Record modified2016-05-09
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