Chalcogen Atoms as Electron Donors in Proton-Coupled Electron Transfer Reactions.

Proton-coupled electron transfer (PCET) reactions are crucial for the optimal functioning of a broad scope of chemical and biological processes. In this report, we present an unprecedented type of concerted PCET (cPCET), in which a chalcogen atom acts as the electron donor. The nature of this mechanism is key for understanding the reactivity of different radical-trapping antioxidants having heavy chalcogens (S, Se, or Te) in their structures. Moreover, this chalcogen-assisted cPCET is likely to be occurring in multiple systems of biological interest.