English
 
Help Privacy Policy Disclaimer
  Advanced SearchBrowse

Item

ITEM ACTIONSEXPORT
  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.

Item is

Basic

show hide
Genre: Journal Article

Files

show Files

Locators

show

Creators

show
hide
 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              

Content

show
hide
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.

Details

show
hide
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: -

Event

show

Legal Case

show

Project information

show

Source 1

show
hide
Title: Chemistry – A European Journal
  Other : Chem. – Eur. J.
  Other : Chem. Eur. J.
Source Genre: Journal
 Creator(s):
Affiliations:
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