Jump to main content
Jump to site search

Issue 13, 2021
Previous Article Next Article

Modulating the radical reactivity of phenyl radicals with the help of distonic charges: it is all about electrostatic catalysis

Author affiliations

Abstract

This manuscript reports the modulation of H-abstraction reactivity of phenyl radicals by (positive and negative) distonic ions. Specifically, we focus on the origins of this modulating effect: can the charged functional groups truly be described as “extreme forms of electron-withdrawing/donating substituents” – implying a through-bond mechanism – as argued in the literature, or is the modulation mainly caused by through-space effects? Our analysis indicates that the effect of the remote charges can be mimicked almost perfectly with the help of a purely electrostatic treatment, i.e. replacing the charged functional groups by a simple uniform electric field is sufficient to recover the quantitative reactivity trends. Hence, through-space effects dominate, whereas through-bond effects play a minor role at best. We elucidate our results through a careful Valence Bond (VB) analysis and demonstrate that such a qualitative analysis not only reveals through-space dominance, but also demonstrates a remarkable reversal in the reactivity trends of a given polarity upon a rational modification of the reaction partner. As such, our findings demonstrate that VB theory can lead to productive predictions about the behaviour of distonic radical ions.

Graphical abstract: Modulating the radical reactivity of phenyl radicals with the help of distonic charges: it is all about electrostatic catalysis

Back to tab navigation

Supplementary files

Article information


Submitted
31 Dec 2020
Accepted
16 Feb 2021
First published
23 Feb 2021

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2021,12, 4800-4809
Article type
Edge Article

Modulating the radical reactivity of phenyl radicals with the help of distonic charges: it is all about electrostatic catalysis

T. Mondal, S. Shaik, H. Kenttämaa and T. Stuyver, Chem. Sci., 2021, 12, 4800 DOI: 10.1039/D0SC07111K

This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence. You can use material from this article in other publications, without requesting further permission from the RSC, provided that the correct acknowledgement is given and it is not used for commercial purposes.

To request permission to reproduce material from this article in a commercial publication, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party commercial publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.


Social activity

Search articles by author

Spotlight

Advertisements