{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,3]],"date-time":"2026-09-03T17:17:31Z","timestamp":1788455851387,"version":"build-2803163510"},"reference-count":105,"publisher":"American Chemical Society (ACS)","issue":"34","license":[{"start":{"date-parts":[[2026,8,21]],"date-time":"2026-08-21T00:00:00Z","timestamp":1787270400000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/100000165","name":"Division of Chemistry","doi-asserted-by":"publisher","award":["CHE-2453754"],"award-info":[{"award-number":["CHE-2453754"]}],"id":[{"id":"10.13039\/100000165","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/100000928","name":"Welch Foundation","doi-asserted-by":"publisher","award":["A-1423"],"award-info":[{"award-number":["A-1423"]}],"id":[{"id":"10.13039\/100000928","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/100000997","name":"Arnold and Mabel Beckman Foundation","doi-asserted-by":"publisher","award":["NA"],"award-info":[{"award-number":["NA"]}],"id":[{"id":"10.13039\/100000997","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/100007904","name":"Texas A and M University","doi-asserted-by":"publisher","award":["NA"],"award-info":[{"award-number":["NA"]}],"id":[{"id":"10.13039\/100007904","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":[],"published-print":{"date-parts":[[2026,9,2]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>The catalytic reduction of oxygen is at the heart of many energy-related and biological processes. Traditionally mediated by transition metals, metal-free systems have emerged as a powerful alternative. In this study, we describe newly prepared quinoline-carbenium species as catalysts for the two-electron reduction of oxygen and show that the quinoline nitrogen atom, depending on its position, can act as a proton relay, thereby boosting the H2O2 production rate. Kinetic studies, H\/D kinetic isotope effect measurements, and cyclic voltammetric investigations support a mechanism that involves intramolecular proton transfer from the protonated quinoline moiety to a carbenium hydroperoxide intermediate in the rate-determining step. Additional kinetic investigations indicate that, in contrast to the proton relaying system, simple carbenium ions use acid from the bulk of the solution to heterolytically cleave the C\u2013O bond of the key carbenium hydroperoxide intermediate. Finally, we uncover the effect of the proton relay on the overpotential, affording an \u03b7eff as low as 80 mV.<\/jats:p>","DOI":"10.1021\/jacs.6c13198","type":"journal-article","created":{"date-parts":[[2026,8,22]],"date-time":"2026-08-22T18:40:52Z","timestamp":1787424052000},"page":"37458-37465","source":"Crossref","is-referenced-by-count":0,"title":["Proton\nRelaying in Carbenium-Based Oxygen Reduction"],"prefix":"10.1021","volume":"148","author":[{"given":"Sean T.","family":"Rooney","sequence":"first","affiliation":[{"name":"Texas A&M University , , , ,","place":["College Station, Texas, United States, 77843"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Mohammadjavad","family":"Karimi","sequence":"additional","affiliation":[{"name":"Texas A&M University , , , ,","place":["College Station, Texas, United States, 77843"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-4788-2998","authenticated-orcid":true,"given":"Franc\u0327ois P.","family":"Gabbai\u0308","sequence":"additional","affiliation":[{"name":"Texas A&M University , , , ,","place":["College Station, Texas, United States, 77843"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,8,21]]},"reference":[{"key":"2026090312075226600_cit1a","doi-asserted-by":"publisher","first-page":"10840","DOI":"10.1021\/acs.chemrev.8b00074","article-title":"Synthetic Fe\/Cu\nComplexes: Toward Understanding Heme-Copper Oxidase Structure and\nFunction","volume":"118","author":"Adam","year":"2018","journal-title":"Chem. Rev."},{"key":"2026090312075226600_cit1b","doi-asserted-by":"publisher","first-page":"2340","DOI":"10.1021\/acs.chemrev.7b00542","article-title":"Oxygen Reduction\nby Homogeneous Molecular Catalysts and Electrocatalysts","volume":"118","author":"Pegis","year":"2018","journal-title":"Chem. Rev."},{"key":"2026090312075226600_cit1c","doi-asserted-by":"publisher","first-page":"561","DOI":"10.1021\/cr0206059","article-title":"Functional Analogues of Cytochrome c Oxidase, Myoglobin, and Hemoglobin","volume":"104","author":"Collman","year":"2004","journal-title":"Chem. Rev."},{"key":"2026090312075226600_cit2a","doi-asserted-by":"publisher","first-page":"932","DOI":"10.1021\/cr9002193","article-title":"Hydrocarbon Hydroxylation\nby Cytochrome\nP450 Enzymes","volume":"110","author":"Ortiz de Montellano","year":"2010","journal-title":"Chem. Rev."},{"key":"2026090312075226600_cit2b","doi-asserted-by":"publisher","first-page":"2253","DOI":"10.1021\/cr0307143","article-title":"Structure\nand Chemistry of Cytochrome P450","volume":"105","author":"Denisov","year":"2005","journal-title":"Chem. Rev."},{"key":"2026090312075226600_cit2c","doi-asserted-by":"publisher","first-page":"561","DOI":"10.2174\/1389200023337054","article-title":"The Cytochrome P450 Superfamily: Biochemistry, Evolution\nand Drug Metabolism in Humans","volume":"3","author":"P B Danielson","year":"2002","journal-title":"Curr. Drug Metab."},{"key":"2026090312075226600_cit3a","doi-asserted-by":"publisher","first-page":"17515","DOI":"10.1021\/jacs.3c02887","article-title":"Optimizing\nthe Synthetic\nPotential of O2: Implications of Overpotential in Homogeneous\nAerobic Oxidation Catalysis","volume":"145","author":"Stamoulis","year":"2023","journal-title":"J. Am. Chem. Soc."},{"key":"2026090312075226600_cit3b","doi-asserted-by":"publisher","first-page":"508","DOI":"10.1002\/cssc.200900020","article-title":"Sustainability in Catalytic Oxidation: An Alternative\nApproach or a Structural Evolution?","volume":"2","author":"Cavani","year":"2009","journal-title":"ChemSusChem"},{"key":"2026090312075226600_cit3c","doi-asserted-by":"publisher","first-page":"2943","DOI":"10.1021\/cr040679f","article-title":"Large-Scale\nOxidations in the Pharmaceutical Industry","volume":"106","author":"Caron","year":"2006","journal-title":"Chem.\nRev."},{"key":"2026090312075226600_cit3d","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202406588","article-title":"Triaryl\nCarbenium Ion Pair Mediated Electrocatalytic Benzylic C\u2013H Oxygenation\nin Air","volume":"63","author":"Zhang","year":"2024","journal-title":"Angew. Chem., Int. Ed."},{"key":"2026090312075226600_cit4a","doi-asserted-by":"publisher","first-page":"222","DOI":"10.1016\/j.ijhydene.2024.12.513","article-title":"Comprehensive review\non the advances and comparisons\nof proton exchange membrane fuel cells (PEMFCs) and anion exchange\nmembrane fuel cells (AFCs): From fundamental principles to key component\ntechnologies","volume":"102","author":"Zeng","year":"2025","journal-title":"Int. J. Hydrogen Energy"},{"key":"2026090312075226600_cit4b","doi-asserted-by":"publisher","first-page":"9301","DOI":"10.1021\/acscatal.5c00903","article-title":"Electrocatalysts for the Oxygen Reduction Reaction\nin Proton Exchange Membrane Fuel Cells: Significant Advances, Major\nChallenges, and Future Directions","volume":"15","author":"Alfaifi","year":"2025","journal-title":"ACS Catal."},{"key":"2026090312075226600_cit4c","doi-asserted-by":"publisher","first-page":"3749","DOI":"10.1021\/acs.chemrev.9b00717","article-title":"Mediated Fuel Cells: Soluble Redox Mediators and Their\nApplications to Electrochemical Reduction of O2 and Oxidation\nof H2, Alcohols, Biomass, and Complex Fuels","volume":"120","author":"Anson","year":"2020","journal-title":"Chem. Rev."},{"key":"2026090312075226600_cit4d","doi-asserted-by":"publisher","first-page":"2392","DOI":"10.1021\/acs.chemrev.7b00220","article-title":"O2 Reduction in Enzymatic\nBiofuel Cells","volume":"118","author":"Mano","year":"2018","journal-title":"Chem. Rev."},{"key":"2026090312075226600_cit4e","doi-asserted-by":"publisher","first-page":"9869","DOI":"10.1021\/acs.chemrev.5b00073","article-title":"Nonstoichiometric\nOxides as Low-Cost and Highly-Efficient Oxygen Reduction\/Evolution\nCatalysts for Low-Temperature Electrochemical Devices","volume":"115","author":"Chen","year":"2015","journal-title":"Chem. Rev."},{"key":"2026090312075226600_cit4f","doi-asserted-by":"publisher","first-page":"3433","DOI":"10.1021\/cr500519c","article-title":"Carbon-Supported Pt-Based Alloy Electrocatalysts\nfor the Oxygen Reduction Reaction in Polymer Electrolyte Membrane\nFuel Cells: Particle Size, Shape, and Composition Manipulation and\nTheir Impact to Activity","volume":"115","author":"Wang","year":"2015","journal-title":"Chem. Rev."},{"key":"2026090312075226600_cit5a","doi-asserted-by":"publisher","first-page":"19302","DOI":"10.1021\/acs.energyfuels.1c02844","article-title":"Progress and Prospects in Redox Mediators for Highly Reversible Lithium\u2013Oxygen\nBatteries: A Minireview","volume":"35","author":"Zhong","year":"2021","journal-title":"Energy Fuels"},{"key":"2026090312075226600_cit5b","doi-asserted-by":"publisher","first-page":"8746","DOI":"10.1039\/C8TA12487F","article-title":"Redox mediators: a shuttle to efficacy\nin metal\u2013O2 batteries","volume":"7","author":"Landa-Medrano","year":"2019","journal-title":"J.\nMater. Chem. A"},{"key":"2026090312075226600_cit5c","doi-asserted-by":"publisher","first-page":"A2274","DOI":"10.1149\/2.0901810jes","article-title":"Review-A Comparative Evaluation of Redox Mediators\nfor Li-O2 Batteries: A Critical Review","volume":"165","author":"Kwak","year":"2018","journal-title":"J. Electrochem. Soc."},{"key":"2026090312075226600_cit6a","doi-asserted-by":"publisher","first-page":"11746","DOI":"10.1039\/D2CC04628H","article-title":"Homogeneous catalysis\nof dioxygen\nreduction by molecular Mn complexes","volume":"58","author":"Cook","year":"2022","journal-title":"Chem. Commun."},{"key":"2026090312075226600_cit6b","doi-asserted-by":"publisher","first-page":"2640","DOI":"10.1021\/acscatal.9b04477","article-title":"Advances\nin the Molecular Catalysis of Dioxygen Reduction","volume":"10","author":"Machan","year":"2020","journal-title":"ACS Catal."},{"key":"2026090312075226600_cit6c","doi-asserted-by":"publisher","first-page":"16458","DOI":"10.1021\/jacs.7b09089","article-title":"Molecular\nCobalt Catalysts for O2 Reduction: Low-Overpotential Production\nof H2O2 and Comparison with Iron-Based Catalysts","volume":"139","author":"Wang","year":"2017","journal-title":"J. Am. Chem. Soc."},{"key":"2026090312075226600_cit6d","doi-asserted-by":"crossref","first-page":"131","DOI":"10.1007\/978-3-319-12415-5_5","article-title":"Transition Metal Complexes and the Activation of\nDioxygen","volume-title":"Sustaining Life on Planet Earth:\nMetalloenzymes Mastering Dioxygen and Other Chewy Gases","author":"Yee","year":"2015"},{"key":"2026090312075226600_cit7a","doi-asserted-by":"publisher","first-page":"30304","DOI":"10.1021\/jacs.5c09566","article-title":"Hydrogen Bonding\nActivates Ferric Porphyrin Hydroperoxo Species and\nDrives the Regioselective Heme Oxygenase Reaction","volume":"147","author":"Roy","year":"2025","journal-title":"J. Am. Chem. Soc."},{"key":"2026090312075226600_cit7b","doi-asserted-by":"publisher","first-page":"6275","DOI":"10.1021\/jacsau.5c01252","article-title":"A Minimalist Iron Porphyrin Which\nCan Catalyze Both Peroxidation and Oxygen Reduction Reaction","volume":"5","author":"Dinda","year":"2025","journal-title":"JACS Au"},{"key":"2026090312075226600_cit7c","doi-asserted-by":"publisher","first-page":"3812","DOI":"10.1021\/jacs.2c13552","article-title":"Amine Groups\nin the Second Sphere of Iron Porphyrins Allow for Higher and Selective\n4e\u2013\/4H+ Oxygen Reduction Rates at Lower Overpotentials","volume":"145","author":"Bhunia","year":"2023","journal-title":"J. Am. Chem. Soc."},{"key":"2026090312075226600_cit7d","doi-asserted-by":"publisher","first-page":"12370","DOI":"10.1021\/acs.chemrev.1c01021","article-title":"Second Sphere\nEffects on Oxygen Reduction and Peroxide Activation by Mononuclear\nIron Porphyrins and Related Systems","volume":"122","author":"Bhunia","year":"2022","journal-title":"Chem. Rev."},{"key":"2026090312075226600_cit8a","doi-asserted-by":"publisher","first-page":"411","DOI":"10.1039\/c0sc00281j","article-title":"Oxygen reduction\nreactivity of cobalt(ii)\nhangman porphyrins","volume":"1","author":"McGuire Jr","year":"2010","journal-title":"Chem. Sci."},{"key":"2026090312075226600_cit8b","doi-asserted-by":"publisher","first-page":"5069","DOI":"10.1021\/ja0683032","article-title":"Proton-Directed\nRedox Control of O\u2013O Bond Activation by Heme Hydroperoxidase\nModels","volume":"129","author":"Soper","year":"2007","journal-title":"J. Am. Chem. Soc."},{"key":"2026090312075226600_cit8c","doi-asserted-by":"publisher","first-page":"7572","DOI":"10.1021\/ic0602087","article-title":"Mechanistic Studies of Hangman Salophen-Mediated Activation\nof O\u2013O Bonds","volume":"45","author":"Liu","year":"2006","journal-title":"Inorg. Chem."},{"key":"2026090312075226600_cit8d","doi-asserted-by":"publisher","first-page":"1866","DOI":"10.1021\/ja028548o","article-title":"Proton-Coupled O-O Activation on\na Redox Platform Bearing a Hydrogen-Bonding Scaffold","volume":"125","author":"Chang","year":"2003","journal-title":"J. Am. Chem. Soc."},{"key":"2026090312075226600_cit8e","doi-asserted-by":"publisher","first-page":"1513","DOI":"10.1021\/ja003245k","article-title":"Hangman\nPorphyrins for the Assembly of a Model Heme Water Channel","volume":"123","author":"Yeh","year":"2001","journal-title":"J. Am. Chem. Soc."},{"key":"2026090312075226600_cit9","doi-asserted-by":"publisher","first-page":"131","DOI":"10.1021\/ja108904s","article-title":"Hangman Corroles: Efficient Synthesis\nand Oxygen Reaction Chemistry","volume":"133","author":"Dogutan","year":"2011","journal-title":"J. Am. Chem.\nSoc."},{"key":"2026090312075226600_cit10","doi-asserted-by":"publisher","first-page":"2421","DOI":"10.1021\/ol034581j","article-title":"Catalytic\nO\u2013O Activation Chemistry\nMediated by Iron Hangman Porphyrins with a Wide Range of Proton-Donating\nAbilities","volume":"5","author":"Chng","year":"2003","journal-title":"Org. Lett."},{"key":"2026090312075226600_cit11a","doi-asserted-by":"publisher","first-page":"10526","DOI":"10.1021\/jp055412e","article-title":"The Poulos\u2013Kraut\nMechanism of Compound I Formation in Horseradish Peroxidase: A QM\/MM\nStudy","volume":"110","author":"Derat","year":"2006","journal-title":"J. Phys. Chem. B"},{"key":"2026090312075226600_cit11b","doi-asserted-by":"publisher","first-page":"27","DOI":"10.1016\/S0162-0134(02)00390-2","article-title":"Mechanisms of compound I formation\nin heme peroxidases","volume":"91","author":"Hiner","year":"2002","journal-title":"J. Inorg. Biochem."},{"key":"2026090312075226600_cit11c","doi-asserted-by":"publisher","first-page":"818","DOI":"10.1021\/ar9502590","article-title":"Investigations\nof the Roles of the Distal Heme Environment and the Proximal Heme\nIron Ligand in Peroxide Activation by Heme Enzymes via Molecular Engineering\nof Myoglobin","volume":"34","author":"Ozaki","year":"2001","journal-title":"Acc. Chem. Res."},{"key":"2026090312075226600_cit11d","doi-asserted-by":"publisher","first-page":"2838","DOI":"10.1074\/jbc.274.5.2838","article-title":"Effects of the Location of Distal Histidine in the\nReaction of Myoglobin with Hydrogen Peroxide","volume":"274","author":"Matsui","year":"1999","journal-title":"J. Biol. Chem."},{"key":"2026090312075226600_cit11e","doi-asserted-by":"publisher","first-page":"10322","DOI":"10.1016\/S0021-9258(19)70467-0","article-title":"A hypothetical model of the cytochrome\nc peroxidase. cytochrome c electron transfer complex","volume":"255","author":"Poulos","year":"1980","journal-title":"J. Biol. Chem."},{"key":"2026090312075226600_cit12a","doi-asserted-by":"publisher","DOI":"10.1002\/cbic.202400750","article-title":"Mechanistic Perspective\non Oxygen Activation Chemistry by Flavoenzymes","volume":"26","author":"Zhang","year":"2025","journal-title":"ChemBioChem"},{"key":"2026090312075226600_cit12b","doi-asserted-by":"publisher","first-page":"1742","DOI":"10.1021\/acs.chemrev.7b00650","article-title":"Same Substrate, Many Reactions: Oxygen\nActivation in Flavoenzymes","volume":"118","author":"Romero","year":"2018","journal-title":"Chem. Rev."},{"key":"2026090312075226600_cit13a","doi-asserted-by":"publisher","first-page":"9363","DOI":"10.1021\/jacs.5b04328","article-title":"Mechanism of Oxygen Activation in\na Flavin-Dependent Monooxygenase: A Nearly Barrierless Formation of\nC4a-Hydroperoxyflavin via Proton-Coupled Electron Transfer","volume":"137","author":"Visitsatthawong","year":"2015","journal-title":"J. Am. Chem. Soc."},{"key":"2026090312075226600_cit13b","doi-asserted-by":"publisher","first-page":"241","DOI":"10.1021\/ja4088055","article-title":"Proton-Coupled\nElectron Transfer and Adduct Configuration Are Important for C4a-Hydroperoxyflavin\nFormation and Stabilization in a Flavoenzyme","volume":"136","author":"Wongnate","year":"2014","journal-title":"J. Am. Chem. Soc."},{"key":"2026090312075226600_cit13c","doi-asserted-by":"publisher","first-page":"28170","DOI":"10.1074\/jbc.M111.241836","article-title":"Stabilization of C4a-Hydroperoxyflavin\nin a Two-component Flavin-dependent Monooxygenase Is Achieved through\nInteractions at Flavin N5 and C4a Atoms","volume":"286","author":"Thotsaporn","year":"2011","journal-title":"J.\nBiol. Chem."},{"key":"2026090312075226600_cit13d","doi-asserted-by":"publisher","first-page":"16900","DOI":"10.1074\/jbc.M111.222976","article-title":"Hydrogen Peroxide Elimination\nfrom C4a-hydroperoxyflavin in a Flavoprotein Oxidase Occurs through\na Single Proton Transfer from Flavin N5 to a Peroxide Leaving Group","volume":"286","author":"Sucharitakul","year":"2011","journal-title":"J. Biol. Chem."},{"key":"2026090312075226600_cit13e","doi-asserted-by":"publisher","first-page":"26","DOI":"10.1016\/j.abb.2009.11.028","article-title":"Control\nof catalysis in flavin-dependent monooxygenases","volume":"493","author":"Palfey","year":"2010","journal-title":"Arch. Biochem. Biophys."},{"key":"2026090312075226600_cit13f","doi-asserted-by":"publisher","first-page":"9697","DOI":"10.1074\/jbc.M109.073247","article-title":"A Conserved\nActive-site Threonine Is Important for Both Sugar and Flavin Oxidations\nof Pyranose 2-Oxidase","volume":"285","author":"Pitsawong","year":"2010","journal-title":"J. Biol. Chem."},{"key":"2026090312075226600_cit13g","doi-asserted-by":"publisher","first-page":"578","DOI":"10.1016\/j.jmb.2010.08.011","article-title":"H-Bonding and Positive\nCharge at the N(5)\/O(4) Locus Are Critical for Covalent Flavin Attachment\nin Trametes Pyranose 2-Oxidase","volume":"402","author":"Tan","year":"2010","journal-title":"J. Mol. Biol."},{"key":"2026090312075226600_cit13h","doi-asserted-by":"publisher","first-page":"8572","DOI":"10.1021\/bi990044o","article-title":"Nature of Oxygen Activation in Glucose\nOxidase from Aspergillus niger: The Importance of Electrostatic Stabilization\nin Superoxide Formation","volume":"38","author":"Su","year":"1999","journal-title":"Biochemistry"},{"key":"2026090312075226600_cit14a","doi-asserted-by":"publisher","first-page":"3122","DOI":"10.1039\/D2CC00110A","article-title":"Activation of O2 across\na C(sp3)\u2013C(sp3) bond","volume":"58","author":"Kumar","year":"2022","journal-title":"Chem. Commun."},{"key":"2026090312075226600_cit14b","doi-asserted-by":"publisher","first-page":"10467","DOI":"10.1021\/acs.joc.1c01120","article-title":"\u03b1,\u03b1\u2032-Diamino-p-tetrafluoroquinodimethane:\nStability of One- and Two-Electron Oxidized Species and Fixation of\nMolecular Oxygen","volume":"86","author":"Mahata","year":"2021","journal-title":"J. Org. Chem."},{"key":"2026090312075226600_cit14c","doi-asserted-by":"publisher","first-page":"3613","DOI":"10.1039\/C9CS00072K","article-title":"Small molecule activation by boron-containing heterocycles","volume":"48","author":"Su","year":"2019","journal-title":"Chem. Soc. Rev."},{"key":"2026090312075226600_cit14d","doi-asserted-by":"publisher","first-page":"2596","DOI":"10.1002\/anie.201511590","article-title":"Stable Boron Peroxides with a Subporphyrinato Ligand","volume":"55","author":"Tsurumaki","year":"2016","journal-title":"Angew. Chem., Int. Ed."},{"key":"2026090312075226600_cit14e","doi-asserted-by":"publisher","first-page":"12893","DOI":"10.1002\/anie.201408462","article-title":"Dioxygen Reactivity\nwith a Ferrocene\u2013Lewis Acid Pairing: Reduction to a Boron Peroxide\nin the Presence of Tris(pentafluorophenyl)borane","volume":"53","author":"Henthorn","year":"2014","journal-title":"Angew. Chem., Int. Ed."},{"key":"2026090312075226600_cit14f","doi-asserted-by":"publisher","first-page":"6186","DOI":"10.1002\/anie.201000520","article-title":"Reaction of\nSinglet Dioxygen with Phosphine-Borane Derivatives: From Transient\nPhosphine Peroxides to Crystalline Peroxoboronates","volume":"49","author":"Porcel","year":"2010","journal-title":"Angew. Chem., Int. Ed."},{"key":"2026090312075226600_cit14g","doi-asserted-by":"publisher","first-page":"3942","DOI":"10.1002\/ejic.200900449","article-title":"Bridging and Terminal\nArrangement of Alkylperoxo Groups in Organoindium Peroxides","volume":"2009","author":"Uhl","year":"2009","journal-title":"Eur. J. Inorg. Chem."},{"key":"2026090312075226600_cit14h","doi-asserted-by":"publisher","first-page":"2767","DOI":"10.1002\/anie.200462503","article-title":"Reversible Binding of Dioxygen by a Non-Transition-Metal\nComplex","volume":"44","author":"Abakumov","year":"2005","journal-title":"Angew. Chem., Int. Ed."},{"key":"2026090312075226600_cit15a","doi-asserted-by":"publisher","first-page":"3032","DOI":"10.1021\/jacsau.5c00516","article-title":"Reductive\nCleavage of Dioxygen Mediated by a Lewis Superacidic Bis(borane)","volume":"5","author":"Escomel","year":"2025","journal-title":"JACS Au"},{"key":"2026090312075226600_cit15b","doi-asserted-by":"publisher","first-page":"2779","DOI":"10.1021\/jacsau.5c00371","article-title":"Direct O2 Activation by Ligand-Constrained\nPnictogen Complexes: Contrasting Mechanisms and OAT Reactivity across\nthe P, Sb, and Bi Triad","volume":"5","author":"Kim","year":"2025","journal-title":"JACS Au"},{"key":"2026090312075226600_cit15c","doi-asserted-by":"publisher","first-page":"11440","DOI":"10.1021\/jacs.4c01748","article-title":"Phosphorus-Ligand\nRedox Cooperative Catalysis: Unraveling Four-Electron Dioxygen Reduction\nPathways and Reactive Intermediates","volume":"146","author":"Kim","year":"2024","journal-title":"J. Am.\nChem. Soc."},{"key":"2026090312075226600_cit15d","doi-asserted-by":"publisher","first-page":"13758","DOI":"10.1021\/jacs.3c02223","article-title":"Four-Electron Reduction of O2 Using Distibines in the Presence of ortho-Quinones","volume":"145","author":"Zhou","year":"2023","journal-title":"J. Am. Chem. Soc."},{"key":"2026090312075226600_cit15e","doi-asserted-by":"publisher","first-page":"11032","DOI":"10.1021\/jacs.7b06772","article-title":"N-Heterocyclic\nCarbene-Stabilized Boranthrene as a Metal-Free Platform for the Activation\nof Small Molecules","volume":"139","author":"Taylor","year":"2017","journal-title":"J. Am. Chem. Soc."},{"key":"2026090312075226600_cit15f","doi-asserted-by":"publisher","first-page":"46","DOI":"10.1021\/acs.inorgchem.5b02580","article-title":"Controlled Oxidation\nof an NHC-Stabilized Phosphinoaminosilylene with Dioxygen","volume":"55","author":"Cui","year":"2016","journal-title":"Inorg. Chem."},{"key":"2026090312075226600_cit15g","doi-asserted-by":"publisher","first-page":"19139","DOI":"10.1021\/ja411667f","article-title":"Splitting Molecular Oxygen en Route\nto a Stable Molecule Containing Diphosphorus Tetroxide","volume":"135","author":"Wang","year":"2013","journal-title":"J. Am. Chem. Soc."},{"key":"2026090312075226600_cit15h","doi-asserted-by":"publisher","first-page":"2187","DOI":"10.1039\/c1dt11774b","article-title":"Synthesis and structural characterization\nof two-coordinate low-valent 14-group metal complexes bearing bulky\nbis(amido)silane ligands","volume":"41","author":"Yang","year":"2012","journal-title":"Dalton Trans."},{"key":"2026090312075226600_cit15i","doi-asserted-by":"publisher","first-page":"577","DOI":"10.1038\/nchem.666","article-title":"From silicon(II)-based dioxygen activation\nto adducts of elusive dioxasiliranes and sila-ureas stable at room\ntemperature","volume":"2","author":"Xiong","year":"2010","journal-title":"Nat. Chem."},{"key":"2026090312075226600_cit15j","doi-asserted-by":"publisher","first-page":"259","DOI":"10.1126\/science.1089145","article-title":"Phosphadioxirane: A\nPeroxide from an Ortho-Substituted Arylphosphine and Singlet Dioxygen","volume":"302","author":"Ho","year":"2003","journal-title":"Science"},{"key":"2026090312075226600_cit16","doi-asserted-by":"publisher","first-page":"757","DOI":"10.1021\/ja02049a006","article-title":"An Instance\nof Trivalent Carbon: Triphenylmethyl","volume":"22","author":"Gomberg","year":"1900","journal-title":"J. Am.\nChem. Soc."},{"key":"2026090312075226600_cit17","doi-asserted-by":"publisher","first-page":"13651","DOI":"10.1021\/jacs.0c04841","article-title":"Bifunctional\nCarbenium Dications as Metal-Free Catalysts\nfor the Reduction of Oxygen","volume":"142","author":"Karimi","year":"2020","journal-title":"J. Am. Chem. Soc."},{"key":"2026090312075226600_cit18","doi-asserted-by":"publisher","first-page":"7931","DOI":"10.1021\/jacs.3c14549","article-title":"Metal-Free\nHomogeneous\nO2 Reduction by an Iminium-Based Electrocatalyst","volume":"146","author":"Cook","year":"2024","journal-title":"J. Am. Chem. Soc."},{"key":"2026090312075226600_cit19","doi-asserted-by":"publisher","first-page":"24892","DOI":"10.1021\/jacs.4c05708","article-title":"Acid Strength\nEffects on Dimerization during Metal-Free Catalytic Dioxygen Reduction","volume":"146","author":"Cook","year":"2024","journal-title":"J. Am. Chem. Soc."},{"key":"2026090312075226600_cit20","doi-asserted-by":"publisher","DOI":"10.1002\/chem.202302854","article-title":"Tunable Metal-Free\nImidazole-Benzimidazole Electrocatalysts for Oxygen Reduction in Aqueous\nSolutions","volume":"30","author":"Tanjedrew","year":"2024","journal-title":"Chem.\u2500Eur. J."},{"key":"2026090312075226600_cit21","doi-asserted-by":"publisher","first-page":"3646","DOI":"10.1021\/ic901550k","article-title":"Role of the Secondary Coordination\nSphere in Metal-Mediated\nDioxygen Activation","volume":"49","author":"Shook","year":"2010","journal-title":"Inorg. Chem."},{"key":"2026090312075226600_cit22a","doi-asserted-by":"publisher","first-page":"1785","DOI":"10.1021\/acs.organomet.4c00258","article-title":"Rh \u2192 Sb Interactions Supported by Tris(8-quinolyl)antimony\nLigands","volume":"43","author":"Wade","year":"2024","journal-title":"Organometallics"},{"key":"2026090312075226600_cit22b","doi-asserted-by":"publisher","first-page":"C56","DOI":"10.1016\/S0022-328X(00)85924-0","article-title":"Organogold Chemistry: IV. Quinolyl- and phenanthridinyl-gold(I)\ncompounds","volume":"190","author":"Vaughan","year":"1980","journal-title":"J. Organomet. Chem."},{"key":"2026090312075226600_cit22c","doi-asserted-by":"publisher","first-page":"1514","DOI":"10.1021\/jo01296a035","article-title":"Facile synthesis of 8-substituted\nquinolines","volume":"45","author":"Suggs","year":"1980","journal-title":"J. Org. Chem."},{"key":"2026090312075226600_cit23","doi-asserted-by":"publisher","first-page":"1553","DOI":"10.1021\/ja01851a018","article-title":"Organometallic Derivatives of Carbazole and Quinoline.\nAmides of 3-Quinoline-carboxylic Acid","volume":"63","author":"Gilman","year":"1941","journal-title":"J. Am.\nChem. Soc."},{"key":"2026090312075226600_cit24","doi-asserted-by":"publisher","first-page":"2275","DOI":"10.1016\/S0040-4039(01)88140-5","article-title":"Polarographische reduktion\nvon triarylmethylkationen","volume":"10","author":"Volz","year":"1969","journal-title":"Tetrahedron Lett."},{"key":"2026090312075226600_cit25a","doi-asserted-by":"publisher","first-page":"11060","DOI":"10.1039\/D0SC04850J","article-title":"Persistent, highly localized, and tunable [4]helicene\nradicals","volume":"11","author":"Shaikh","year":"2020","journal-title":"Chem. Sci."},{"key":"2026090312075226600_cit25b","doi-asserted-by":"publisher","first-page":"9","DOI":"10.1021\/acsaem.0c02350","article-title":"Symmetric, Robust,\nand High-Voltage Organic Redox Flow Battery Model Based on a Helical\nCarbenium Ion Electrolyte","volume":"4","author":"Moutet","year":"2021","journal-title":"ACS Appl. Energy\nMater."},{"key":"2026090312075226600_cit25c","doi-asserted-by":"publisher","first-page":"216","DOI":"10.1039\/D1MA00914A","article-title":"Increased\nperformance of an all-organic redox flow battery model via nitration\nof the [4]helicenium DMQA ion electrolyte","volume":"3","author":"Moutet","year":"2022","journal-title":"Mater.\nAdv."},{"key":"2026090312075226600_cit26a","doi-asserted-by":"publisher","first-page":"1269","DOI":"10.1021\/acs.organomet.8b00548","article-title":"Electrocatalytic Hydrogen Production\nby a Nickel Complex Containing a Tetradentate Phosphine Ligand","volume":"38","author":"Klug","year":"2019","journal-title":"Organometallics"},{"key":"2026090312075226600_cit26b","doi-asserted-by":"publisher","first-page":"2275","DOI":"10.1021\/acs.organomet.7b00103","article-title":"Impact of Weak Agostic\nInteractions in Nickel Electrocatalysts for Hydrogen Oxidation","volume":"36","author":"Klug","year":"2017","journal-title":"Organometallics"},{"key":"2026090312075226600_cit26c","doi-asserted-by":"publisher","first-page":"604","DOI":"10.1021\/jacs.5b10853","article-title":"Kinetic Analysis of Competitive Electrocatalytic Pathways:\nNew Insights into Hydrogen Production with Nickel Electrocatalysts","volume":"138","author":"Wiedner","year":"2016","journal-title":"J. Am. Chem. Soc."},{"key":"2026090312075226600_cit26d","doi-asserted-by":"publisher","first-page":"2527","DOI":"10.1021\/cs400638f","article-title":"Hydrogen Production\nUsing Nickel Electrocatalysts with Pendant Amines: Ligand Effects\non Rates and Overpotentials","volume":"3","author":"Wiese","year":"2013","journal-title":"ACS Catal."},{"key":"2026090312075226600_cit26e","doi-asserted-by":"publisher","first-page":"9700","DOI":"10.1021\/ja400705a","article-title":"Two Pathways for Electrocatalytic Oxidation of Hydrogen\nby a Nickel Bis(diphosphine) Complex with Pendant Amines in the Second\nCoordination Sphere","volume":"135","author":"Yang","year":"2013","journal-title":"J. Am. Chem. Soc."},{"key":"2026090312075226600_cit27","doi-asserted-by":"publisher","first-page":"12852","DOI":"10.1002\/ange.202102523","article-title":"Controlling Oxygen Reduction Selectivity through Steric Effects:\nElectrocatalytic Two-Electron and Four-Electron Oxygen Reduction with\nCobalt Porphyrin Atropisomers","volume":"133","author":"Lv","year":"2021","journal-title":"Angew. Chem."},{"key":"2026090312075226600_cit28a","doi-asserted-by":"publisher","first-page":"11821","DOI":"10.1021\/ja506193v","article-title":"Pendant Acid\u2013Base Groups in Molecular Catalysts:\nH-Bond Promoters or Proton Relays? Mechanisms of the Conversion of\nCO2 to CO by Electrogenerated Iron(0)Porphyrins Bearing\nPrepositioned Phenol Functionalities","volume":"136","author":"Costentin","year":"2014","journal-title":"J. Am.\nChem. Soc."},{"key":"2026090312075226600_cit28b","doi-asserted-by":"publisher","first-page":"90","DOI":"10.1126\/science.1224581","article-title":"A Local\nProton Source Enhances CO2 Electroreduction to CO by a\nMolecular Fe Catalyst","volume":"338","author":"Costentin","year":"2012","journal-title":"Science"},{"key":"2026090312075226600_cit29a","doi-asserted-by":"publisher","first-page":"809","DOI":"10.1021\/jacs.5c16378","article-title":"Highly Acidic Second Coordination Spheres Promote In\nSitu Formation of Iron Phlorins Exhibiting Fast and Selective CO2 Reduction","volume":"148","author":"Teindl","year":"2026","journal-title":"J. Am. Chem. Soc."},{"key":"2026090312075226600_cit29b","doi-asserted-by":"publisher","first-page":"17176","DOI":"10.1021\/jacs.3c03919","article-title":"Linear Free Energy\nRelationships and Transition State Analysis of CO2 Reduction\nCatalysts Bearing Second Coordination Spheres with Tunable Acidity","volume":"145","author":"Teindl","year":"2023","journal-title":"J. Am. Chem. Soc."},{"key":"2026090312075226600_cit30","doi-asserted-by":"publisher","first-page":"630","DOI":"10.1021\/cs401013v","article-title":"Determining the Overpotential for a Molecular Electrocatalyst","volume":"4","author":"Appel","year":"2014","journal-title":"ACS Catal."},{"key":"2026090312075226600_cit31a","doi-asserted-by":"publisher","first-page":"1219","DOI":"10.1021\/acs.organomet.8b00334","article-title":"Carbon Dioxide Reduction by Iron\nHangman Porphyrins","volume":"38","author":"Margarit","year":"2019","journal-title":"Organometallics"},{"key":"2026090312075226600_cit31b","doi-asserted-by":"publisher","first-page":"850","DOI":"10.1021\/acscentsci.6b00261","article-title":"Homogenous\nElectrocatalytic Oxygen Reduction Rates Correlate with Reaction Overpotential\nin Acidic Organic Solutions","volume":"2","author":"Pegis","year":"2016","journal-title":"ACS Cent. Sci."},{"key":"2026090312075226600_cit31c","doi-asserted-by":"publisher","first-page":"5285","DOI":"10.1021\/acs.inorgchem.5b00233","article-title":"Design of a Catalytic Active Site for Electrochemical\nCO2 Reduction with Mn(I)-Tricarbonyl Species","volume":"54","author":"Agarwal","year":"2015","journal-title":"Inorg. Chem."},{"key":"2026090312075226600_cit32","doi-asserted-by":"publisher","first-page":"9983","DOI":"10.1021\/ic500658x","article-title":"Evaluation of Homogeneous\nElectrocatalysts by Cyclic Voltammetry","volume":"53","author":"Rountree","year":"2014","journal-title":"Inorg.\nChem."},{"key":"2026090312075226600_cit33","doi-asserted-by":"publisher","first-page":"1652","DOI":"10.1021\/ja02253a013","article-title":"Triphenylmethyl.\nXXVII. The Molecular Weights of the\nTriarylmethyls","volume":"39","author":"Gomberg","year":"1917","journal-title":"J. Am. Chem. Soc."},{"key":"2026090312075226600_cit34","doi-asserted-by":"publisher","first-page":"2512","DOI":"10.1021\/ja00425a020","article-title":"Stable carbocations.\n194. Patterns\nof carbon-13 chemical shift response to substituent effects in arylcarbenium\nions. The phenyl, phenylethynyl, and naphthyl systems","volume":"98","author":"Forsyth","year":"1976","journal-title":"J. Am. Chem. Soc."},{"key":"2026090312075226600_cit35a","doi-asserted-by":"publisher","first-page":"4095","DOI":"10.1039\/D3SC06753J","article-title":"Catalytic reduction\nof oxygen to water by non-heme iron complexes: exploring the effect\nof the secondary coordination sphere proton exchanging site","volume":"15","author":"Santra","year":"2024","journal-title":"Chem. Sci."},{"key":"2026090312075226600_cit35b","doi-asserted-by":"publisher","first-page":"560","DOI":"10.1021\/jacs.0c09106","article-title":"Proton-Coupled\nElectron Transfer Guidelines, Fair and Square","volume":"143","author":"Tyburski","year":"2021","journal-title":"J. Am. Chem. Soc."},{"key":"2026090312075226600_cit35c","doi-asserted-by":"publisher","first-page":"17350","DOI":"10.1021\/jacs.9b09062","article-title":"The Role of Proton\nShuttles in the Reversible Activation of Hydrogen via Metal\u2013Ligand\nCooperation","volume":"141","author":"Smith","year":"2019","journal-title":"J. Am. Chem. Soc."},{"key":"2026090312075226600_cit36","doi-asserted-by":"publisher","first-page":"48","DOI":"10.1002\/1521-3773(20020104)41:1&lt;48::AID-ANIE48&gt;3.0.CO;2-U","article-title":"The Hydrogen\nBond in the Solid State","volume":"41","author":"Steiner","year":"2002","journal-title":"Angew. Chem., Int.\nEd."},{"key":"2026090312075226600_cit37a","doi-asserted-by":"publisher","first-page":"139","DOI":"10.10520\/AJA03794350_2051","article-title":"Synthesis\nof hydrogen peroxide: acid-catalysed decomposition of 9-hydroperoxy-9-phenylxanthene\nand its derivatives","volume":"40","author":"Taljaard","year":"1987","journal-title":"S. Afr. J. Chem."},{"key":"2026090312075226600_cit37b","doi-asserted-by":"publisher","first-page":"164","DOI":"10.10520\/AJA03794350_1491","article-title":"Stable hydroperoxide synthesis","volume":"37","author":"Glover","year":"1984","journal-title":"S. Afr. J. Chem."},{"key":"2026090312075226600_cit38","doi-asserted-by":"publisher","first-page":"1804","DOI":"10.1002\/(sici)1521-3773(20000515)39:10&lt;1804::aid-anie1804&gt;3.0.co;2-3","article-title":"Preparation, structure,\nand redox reactions of nine-membered cyclic peroxides: a novel electrochromic\nsystem undergoing reversible extrusion and trapping of O2","volume":"39","author":"Suzuki","year":"2000","journal-title":"Angew. Chem., Int. Ed."}],"container-title":["Journal of the American Chemical Society"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/pubs.acs.org\/doi\/pdf\/10.1021\/jacs.6c13198","content-type":"application\/pdf","content-version":"vor","intended-application":"unspecified"},{"URL":"https:\/\/pubs.acs.org\/jacsat\/article-pdf\/148\/34\/37458\/66997545\/jacs.6c13198.pdf","content-type":"application\/pdf","content-version":"vor","intended-application":"syndication"},{"URL":"https:\/\/pubs.acs.org\/jacsat\/article-pdf\/148\/34\/37458\/66997545\/jacs.6c13198.pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,9,3]],"date-time":"2026-09-03T16:25:57Z","timestamp":1788452757000},"score":1,"resource":{"primary":{"URL":"https:\/\/pubs.acs.org\/jacsat\/article\/148\/34\/37458\/5286806\/Proton-Relaying-in-Carbenium-Based-Oxygen"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2026,8,21]]},"references-count":105,"journal-issue":{"issue":"34","published-online":{"date-parts":[[2026,8,21]]},"published-print":{"date-parts":[[2026,9,2]]}},"URL":"https:\/\/doi.org\/10.1021\/jacs.6c13198","relation":{},"ISSN":["0002-7863","1520-5126"],"issn-type":[{"value":"0002-7863","type":"print"},{"value":"1520-5126","type":"electronic"}],"subject":[],"published":{"date-parts":[[2026,8,21]]}}}