Universität zu Köln

Verschueren, Rik H., Schmauck, Julie, Perryman, Michael S., Yue, Hui-Lan, Riegger, Julian, Schweitzer-Chaput, Bertrand ORCID: 0000-0003-2105-6233, Breugst, Martin ORCID: 0000-0003-0950-8858 and Klussmann, Martin ORCID: 0000-0002-9026-205X (2019). Philicity of Acetonyl and Benzoyl Radicals: A Comparative Experimental and Computational Study. Chem.-Eur. J., 25 (38). S. 9088 - 9098. WEINHEIM: WILEY-V C H VERLAG GMBH. ISSN 1521-3765

Full text not available from this repository.

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 (sigma(+)) 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.

Item Type:	Journal Article
Creators:	Creators Email ORCID ORCID Put Code Verschueren, Rik H. UNSPECIFIED UNSPECIFIED UNSPECIFIED Schmauck, Julie UNSPECIFIED UNSPECIFIED UNSPECIFIED Perryman, Michael S. UNSPECIFIED UNSPECIFIED UNSPECIFIED Yue, Hui-Lan UNSPECIFIED UNSPECIFIED UNSPECIFIED Riegger, Julian UNSPECIFIED UNSPECIFIED UNSPECIFIED Schweitzer-Chaput, Bertrand UNSPECIFIED orcid.org/0000-0003-2105-6233 UNSPECIFIED Breugst, Martin UNSPECIFIED orcid.org/0000-0003-0950-8858 UNSPECIFIED Klussmann, Martin UNSPECIFIED orcid.org/0000-0002-9026-205X UNSPECIFIED
URN:	urn:nbn:de:hbz:38-135420
DOI:	10.1002/chem.201901439
Journal or Publication Title:	Chem.-Eur. J.
Volume:	25
Number:	38
Page Range:	S. 9088 - 9098
Date:	2019
Publisher:	WILEY-V C H VERLAG GMBH
Place of Publication:	WEINHEIM
ISSN:	1521-3765
Language:	English
Faculty:	Faculty of Mathematics and Natural Sciences
Divisions:	Faculty of Mathematics and Natural Sciences > Department of Chemistry > Institute of Organic Chemistry
Subjects:	no entry
Uncontrolled Keywords:	Keywords Language CARBON-CENTERED RADICALS; CATALYZED CARBONYLATION-PEROXIDATION; DOUBLE-BONDS; SUBSTITUENT CONSTANTS; HOMOLYTIC ACYLATION; MOLECULAR-ENERGIES; AROMATIC-COMPOUNDS; REACTIVITY; ALKENES; POLAR Multiple languages Chemistry, Multidisciplinary Multiple languages
Refereed:	Yes
URI:	http://kups.ub.uni-koeln.de/id/eprint/13542