Regioselective S-O vs. C-O bond cleavage in sulfenate ester radical anions1

The electron transfer (ET) reduction of benzyl benzenesulfenate ester (1) and tert-buty1 benzenesulfenate ester (2) was investigated using electrochemical techniques. Analysis of the cyclic voltammetry of each compound suggests that the ET reduction proceeds via a stepwise dissociative mechanism. Th...

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Bibliographic Details
Published inCanadian journal of chemistry Vol. 83; no. 9; p. 1473
Main Authors Stringle, Donald L B, Workentin, Mark S
Format Journal Article
LanguageEnglish
Published Ottawa Canadian Science Publishing NRC Research Press 01.09.2005
Subjects
Anions
Chemical bonds
Chemical compounds
Electrochemistry
Electrolysis
Electron transfer reactions
Free radicals
Ions
Oxidation
Perchlorate
Studies
Voltammetry
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Summary:The electron transfer (ET) reduction of benzyl benzenesulfenate ester (1) and tert-buty1 benzenesulfenate ester (2) was investigated using electrochemical techniques. Analysis of the cyclic voltammetry of each compound suggests that the ET reduction proceeds via a stepwise dissociative mechanism. The voltammograms of 1 are similar to those of diaryl disulfides and it was found through controlled potential electrolysis (CPE) product studies that ET reduction leads to S-O bond cleavage. The voltammograms of 2 are dramatically different with a sharper dissociative wave occurring at a more negative peak potential. CPE experiments indicate products that result from ET leading to C-O bond cleavage in this case. DFT calculations of the singly occupied molecular orbitals (SOMOs) of 1 and 2 were performed and offer a rationale for the different reactivity of the two radical anions. [PUBLICATION ABSTRACT]
ISSN:0008-4042
1480-3291