Net fluorine atom transfer from the perspective of a PCET chemist

Abstract

Proton coupled electron transfer (PCET) reactions, which encompass hydrogen atom transfer (HAT), concerted proton coupled electron transfer (cPCET) and stepwise variations, have been studied in great detail. This has facilitated the thorough understanding of relevant enzymatic transformations and the efficient development of synthetic strategies. Despite the clear similarities between halogen atom transfer (XAT) and HAT, the conceptual framework used within the PCET community has not yet been extended to radical halogen reactivities. In light of a recent report showing that net homolytic C–F bond cleavage can proceed through a concerted electron fluoride transfer (cEFT) mechanism, we wish to encourage the adoption of a systematic framework for the analysis of radical halogen reactivity, similar to that employed for PCET reactions.