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  1. Free, publicly-accessible full text available February 1, 2024
  2. The two-electron and two-proton p -hydroquinone/ p -benzoquinone (H 2 Q/BQ) redox couple has mechanistic parallels to the function of ubiquinone in the electron transport chain. This proton-dependent redox behavior has shown applicability in catalytic aerobic oxidation reactions, redox flow batteries, and co-electrocatalytic oxygen reduction. Under nominally aprotic conditions in non-aqueous solvents, BQ can be reduced by up to two electrons in separate electrochemically reversible reactions. With weak acids (AH) at high concentrations, potential inversion can occur due to favorable hydrogen-bonding interactions with the intermediate monoanion [BQ(AH) m ]˙ − . The solvation shell created by these interactions can mediate a second one-electron reduction coupled to proton transfer at more positive potentials ([BQ(AH) m ]˙ − + n AH + e − ⇌ [HQ(AH) (m+n)−1 (A)] 2− ), resulting in an overall two electron reduction at a single potential at intermediate acid concentrations. Here we show that hydrogen-bonded adducts of reduced quinones and the proton donor 2,2,2-trifluoroethanol (TFEOH) can mediate the transfer of electrons to a Mn-based complex during the electrocatalytic reduction of dioxygen (O 2 ). The Mn electrocatalyst is selective for H 2 O 2 with only TFEOH and O 2 present, however, with BQ present under sufficientmore »concentrations of TFEOH, an electrogenerated [H 2 Q(AH) 3 (A) 2 ] 2− adduct (where AH = TFEOH) alters product selectivity to 96(±0.5)% H 2 O in a co-electrocatalytic fashion. These results suggest that hydrogen-bonded quinone anions can function in an analogous co-electrocatalytic manner to H 2 Q.« less