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  Philicity of Acetonyl and Benzoyl Radicals: A Comparative Experimental and Computational Study

Verschueren, R. H., Schmauk, J., Perryman, M. S., Yue, H.-L., Riegger, J., Schweitzer-Chaput, B., et al. (2019). Philicity of Acetonyl and Benzoyl Radicals: A Comparative Experimental and Computational Study. Chemistry – A European Journal, 25(38), 9088-9097. doi:10.1002/chem.201901439.

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 Creators:
Verschueren, Rik H.1, Author           
Schmauk, Julie2, Author
Perryman, Michael S.1, Author           
Yue, Hui-Lan1, Author           
Riegger, Julian1, Author           
Schweitzer-Chaput, Bertrand1, Author           
Breugst, Martin2, Author
Klussmann, Martin1, Author           
Affiliations:
1Research Group Klußmann, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1445608              
2Department für Chemie, Universität zu Köln, Greinstraße 4, 50939 Köln, Germany, ou_persistent22              

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Free keywords: aromatic substitution; linear free-energy relationships; philicity; radicals; substituent effects
 Abstract: In this work, the reactivities of acetonyl and benzoyl radicals in aromatic substitution and addition reactions have been compared in an experimental and computational study. The results show that acetonyl is more electrophilic than benzoyl, which is rather nucleophilic. A Hammett plot analysis of the addition reactions of the two radicals to substituted styrenes clearly support the nucleophilicity of benzoyl, but in the case of acetonyl, no satisfactory linear correlation with a single substituent‐related parameter was found. Computational calculations helped to rationalize this effect, and a good linear correlation was found with a combination of polar parameters (σ+) and the radical stabilization energies of the formed intermediates. Based on the calculated philicity indices for benzoyl and acetonyl, a quantitative comparison of these two radicals with many other reported radicals is possible, which may help to predict the reactivities of other aromatic radical substitution reactions.

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Language(s): eng - English
 Dates: 2019-03-272019-05-022019-07-05
 Publication Status: Published online
 Pages: 10
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1002/chem.201901439
 Degree: -

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Title: Chemistry – A European Journal
  Other : Chem. – Eur. J.
  Other : Chem. Eur. J.
Source Genre: Journal
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Publ. Info: Weinheim : Wiley-VCH
Pages: - Volume / Issue: 25 (38) Sequence Number: - Start / End Page: 9088 - 9097 Identifier: ISSN: 0947-6539
CoNE: https://pure.mpg.de/cone/journals/resource/954926979058