1. bookVolume 5 (2012): Issue 1 (April 2012)
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eISSN
1339-3065
ISSN
1337-978X
First Published
10 Dec 2012
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2 times per year
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English
access type Open Access

S—H Bond Dissociation Enthalpies in para- and meta-Substituted Thiophenols: Correlation with Thiophenolic C—S Bond Length

Published Online: 14 May 2012
Volume & Issue: Volume 5 (2012) - Issue 1 (April 2012)
Page range: 37 - 41
Journal Details
License
Format
Journal
eISSN
1339-3065
ISSN
1337-978X
First Published
10 Dec 2012
Publication timeframe
2 times per year
Languages
English
S—H Bond Dissociation Enthalpies in <italic>para</italic>- and <italic>meta</italic>-Substituted Thiophenols: Correlation with Thiophenolic C—S Bond Length

For mono-substituted anilines, phenols, and thiophenols it has been found that N—H, O—H and S—H bond dissociation enthalpies (BDE) depend on Hammett constants approximately linearly. For substituents placed in meta position, linearity of found dependences is usually considerably worse in comparison to para-substituted molecules. Therefore, their applicability for prediction of changes in BDE using substituent Hammett constant may be limited. In this work, we have found that the length of thiophenolic C—S bond, R(C—S), or its shortening after hydrogen atom abstraction, ΔR(C—S), represent suitable descriptors of substituent induced changes in S—H BDE. For fifteen studied meta-substituted thiophenols, these geometry descriptors correlate with S—H BDEs considerably better than Hammett constants.

Keywords

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