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

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

SUBMITTER: Mondal T 

PROVIDER: S-EPMC8179573 | biostudies-literature | 2021 Feb

REPOSITORIES: biostudies-literature