Therefore, the one-electron reduction of the preformed complex (O2-RsvH3) is assumed to result in the formation of various HB complexes involving O2 •--RsvH3 composed of the free reactants, O2 •-, HO2 • , RsvH3, and RsvH2 -. First, we scanned some plausible PRCs formed with a combination of these free reactants (step i). Then, the stable intermediate HB-complex, TS, and PC, along with the subsequent PCET reaction were scanned (Supporting Information, Table ).