Peroxide-Selective Reduction of O₂ at Redox-Inactive Rare-Earth(III) Triflates Generates an Ambiphilic Peroxide

Metal peroxides are key species involved in a range of critical biological and synthetic processes. Rare-earth (group III and the lanthanides; Sc, Y, La–Lu) peroxides have been implicated as reactive intermediates in catalysis; however, reactivity studies of isolated, structurally characterized rare-earth peroxides have been limited. Herein, we report the peroxide-selective (93–99% O₂^2‑) reduction of dioxygen (O₂) at redox-inactive rare-earth triflates in methanol using a mild metallocene reductant, decamethylferrocene (Fc*). The first molecular praseodymium peroxide ([Pr^III₂(O₂^2–)­(18C6)₂(EG)₂]­[OTf]₄; 18C6 = 18-crown-6, EG = ethylene glycol, ^–OTf = ^–O₃SCF₃; <b>2-Pr</b>) was isolated and characterized by single-crystal X-ray diffraction, Raman spectroscopy, and NMR spectroscopy. <b>2-Pr</b> displays high thermal stability (120 °C, 50 mTorr), is protonated by mild organic acids [p<i>K</i>_a1(MeOH) = 5.09 ± 0.23], and engages in electrophilic (e.g., oxygen atom transfer) and nucleophilic (e.g., phosphate-ester cleavage) reactivity. Our mechanistic studies reveal that the rate of oxygen reduction is dictated by metal-ion accessibility, rather than Lewis acidity, and suggest new opportunities for differentiated reactivity of redox-inactive metal ions by leveraging weak metal–ligand binding events preceding electron transfer.