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

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, 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.