{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,3,25]],"date-time":"2026-03-25T10:50:14Z","timestamp":1774435814645,"version":"3.50.1"},"reference-count":31,"publisher":"Wiley","issue":"21","license":[{"start":{"date-parts":[[2025,9,21]],"date-time":"2025-09-21T00:00:00Z","timestamp":1758412800000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100001665","name":"ANR","doi-asserted-by":"publisher","award":["DeNOSOr project ANR\u201022\u2010CE07\u20100028\u201001"],"award-info":[{"award-number":["DeNOSOr project ANR\u201022\u2010CE07\u20100028\u201001"]}],"id":[{"id":"10.13039\/501100001665","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["chemistry-europe.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["ChemPhysChem"],"published-print":{"date-parts":[[2025,11,5]]},"abstract":"<jats:p>Electrochemical reductive deoxygenation of pyridine N\u2010oxide is investigated with particular focus on the role of proton\u2010coupled electron transfers. A detailed analysis of cyclic voltammograms reveals that the initial electron transfer is followed by protonation of the pyridine N\u2010oxide anion radical. Kinetic analysis reveals an unusual fifth\u2010order dependence on the concentration of the proton donor (either water or ethanol), suggesting the involvement of a proton donor cluster in the protonation step. The resulting neutral radical represents a key bottleneck in the reaction pathway, as it can proceed via either a parent\u2010child coupling reaction or N\uf8ffO bond cleavage, the latter leading to the formation of pyridine. This competition between reaction pathways allows extraction of both the rate constant for the protonation of the N\u2010oxide radical anion and kinetic information related to the reductive N\uf8ffO bond cleavage. The reductive cleavage of the protonated N\u2010oxide radical may proceed via two possible mechanisms: 1) homolytic bond cleavage followed by reduction of the hydroxyl radical, or 2) a concerted dissociative electron transfer. The observed hydrogen\u2010bonding effects, combined with the higher driving force for the concerted pathway, support the latter mechanism, where stabilization of the departing hydroxide ion facilitates the electron transfer.<\/jats:p>","DOI":"10.1002\/cphc.202500292","type":"journal-article","created":{"date-parts":[[2025,9,22]],"date-time":"2025-09-22T00:39:29Z","timestamp":1758501569000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":1,"title":["Proton\u2010Coupled Electron Transfer Deoxygenation of Pyridine N\u2010Oxide: A Mechanistic Study"],"prefix":"10.1002","volume":"26","author":[{"given":"C\u00e9line","family":"Naddour","sequence":"first","affiliation":[{"name":"Universit\u00e9 Grenoble Alpes, DCM, CNRS  38000 Grenoble France"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-1836-6142","authenticated-orcid":false,"given":"Gabriel","family":"Durin","sequence":"additional","affiliation":[{"name":"Universit\u00e9 Grenoble Alpes, DCM, CNRS  38000 Grenoble France"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-0273-1571","authenticated-orcid":false,"given":"Sylvie","family":"Chardon\u2010Noblat","sequence":"additional","affiliation":[{"name":"Universit\u00e9 Grenoble Alpes, DCM, CNRS  38000 Grenoble France"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7098-3132","authenticated-orcid":false,"given":"Cyrille","family":"Costentin","sequence":"additional","affiliation":[{"name":"Universit\u00e9 Grenoble Alpes, DCM, CNRS  38000 Grenoble France"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2025,9,21]]},"reference":[{"key":"e_1_2_10_2_1","doi-asserted-by":"publisher","DOI":"10.1246\/bcsj.35.1549"},{"key":"e_1_2_10_3_1","doi-asserted-by":"publisher","DOI":"10.1002\/bscb.19670760307"},{"key":"e_1_2_10_4_1","doi-asserted-by":"publisher","DOI":"10.1016\/0013-4686(88)80194-4"},{"key":"e_1_2_10_5_1","doi-asserted-by":"publisher","DOI":"10.1016\/0022-0728(90)80062-B"},{"key":"e_1_2_10_6_1","doi-asserted-by":"publisher","DOI":"10.1055\/s-0034-1379884"},{"key":"e_1_2_10_7_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.orglett.8b03446"},{"key":"e_1_2_10_8_1","doi-asserted-by":"publisher","DOI":"10.1002\/adsc.202200200"},{"key":"e_1_2_10_9_1","doi-asserted-by":"publisher","DOI":"10.1039\/D1SC01974K"},{"key":"e_1_2_10_10_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.orglett.9b04632"},{"key":"e_1_2_10_11_1","first-page":"3755","volume":"19","author":"Kim S. 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