Understanding (the lack of) homolytic substitution chemistry of sulfones

High level calculations suggest that homolytic substitution (S(H)2) by alkyl radicals at sulfur proceeds through a mechanism that is assisted and dominated by LP → SOMO interactions; in the absence of these interactions, S(H)2 chemistry at sulfur is predicted to be virtually impossible. G3(MP2)-RAD...

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Published inChemical communications (Cambridge, England) Vol. 48; no. 67; pp. 8326 - 8328
Main Authors Aitken, Heather M, Hancock, Amber N, Schiesser, Carl H
Format Journal Article
LanguageEnglish
Published England 28.08.2012
Subjects
Cyclization
Free Radicals
Models, Molecular
Molecular Structure
Sulfones - chemistry
Sulfur - chemistry
Thermodynamics
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Summary:High level calculations suggest that homolytic substitution (S(H)2) by alkyl radicals at sulfur proceeds through a mechanism that is assisted and dominated by LP → SOMO interactions; in the absence of these interactions, S(H)2 chemistry at sulfur is predicted to be virtually impossible. G3(MP2)-RAD calculations suggest that cyclization of the tert-butylsulfonylbutyl radical 2 (n = 2) proceeds with a rate constant of 1.7 × 10(-24) s(-1) at 80°, some 28 orders of magnitude slower than its sulfide cousin (n = 0).
Bibliography:ObjectType-Article-1
SourceType-Scholarly Journals-1
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ISSN:1359-7345
1364-548X
DOI:10.1039/c2cc33856d