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

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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

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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, Advance Article
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, Advance Article , DOI: 10.1039/D0SC07111K

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