{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,19]],"date-time":"2026-10-19T19:44:02Z","timestamp":1792439042231,"version":"4.5.0"},"reference-count":109,"publisher":"Wiley","issue":"31","license":[{"start":{"date-parts":[[2025,6,30]],"date-time":"2025-06-30T00:00:00Z","timestamp":1751241600000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100001659","name":"Deutsche Forschungsgemeinschaft","doi-asserted-by":"publisher","id":[{"id":"10.13039\/501100001659","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Angew Chem Int Ed"],"published-print":{"date-parts":[[2025,7,28]]},"abstract":"Abstract<\/jats:title>\n \n We compare the carbon dioxide reduction (CO\n 2<\/jats:sub>\n RR) activity and selectivity of the complexes [\n \n (Hbbpya)Co\n II<\/jats:sup>\n <\/jats:bold>\n ]\n \n 2+<\/jats:sup>\n <\/jats:bold>\n and [\n \n (Mebbpya)Co\n II<\/jats:sup>\n <\/jats:bold>\n ]\n \n 2+<\/jats:sup>\n <\/jats:bold>\n , which contain two 2,2\u2032\u2010bipyridine chelating groups linked by \u2010NH or \u2010NCH\n 3<\/jats:sub>\n moieties, respectively. Whereas [\n \n (Hbbpya)Co\n II<\/jats:sup>\n <\/jats:bold>\n ]\n \n 2+<\/jats:sup>\n <\/jats:bold>\n forms CO under electrocatalytic conditions in presence of phenol (PhOH) with high selectivity, [\n \n (Mebbpya)Co\n II<\/jats:sup>\n <\/jats:bold>\n ]\n \n 2+<\/jats:sup>\n <\/jats:bold>\n shows higher hydrogen evolution reaction activity and low selectivity for CO production. The molecular origin of the difference in product selectivity was analysed based on spectroscopic trapping of reactive intermediates and detailed kinetic and theoretical studies. A difference in mechanism is evident; whereas an efficient proton relay mediated by the \u2010NH group initiates a two\u2010electron reduction of CO\n 2<\/jats:sub>\n in the case of [\n \n (Hbbpya)Co\n II<\/jats:sup>\n <\/jats:bold>\n ]\n \n 2+<\/jats:sup>\n <\/jats:bold>\n , one\u2010electron chemistry prevails for [\n \n (Mebbpya)Co\n II<\/jats:sup>\n <\/jats:bold>\n ]\n \n 2+<\/jats:sup>\n <\/jats:bold>\n . Under stopped\u2010flow conditions, we trapped the one\u2010electron reduced CO\n 2<\/jats:sub>\n radical anion in [\n \n (Mebbpya)Co\n I<\/jats:sup>\n (CO\n 2<\/jats:sub>\n \u2212\u2022<\/jats:sup>\n )\n <\/jats:bold>\n ], which forms oxalate under aprotic conditions. This study underlines the importance of subtle electronic and protonation changes in controlling the CO\n 2<\/jats:sub>\n RR product selectivity.\n <\/jats:p>","DOI":"10.1002\/anie.202503705","type":"journal-article","created":{"date-parts":[[2025,5,21]],"date-time":"2025-05-21T03:29:34Z","timestamp":1747798174000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":7,"title":["Mechanistic Promiscuity in Cobalt\u2010Mediated CO\n 2<\/sub>\n Reduction Reaction: One\u2010 Versus Two\u2010Electron Reduction Process"],"prefix":"10.1002","volume":"64","author":[{"given":"Ayan","family":"Bera","sequence":"first","affiliation":[{"name":"Institut f\u00fcr Chemie, Humboldt\u2010Universit\u00e4t zu Berlin Brook\u2010Taylor\u2010Str. 2 12489 Berlin Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Sarah","family":"Bimmermann","sequence":"additional","affiliation":[{"name":"Faculty of Chemistry & Biochemistry, Ruhr\u2010Universit\u00e4t Bochum, Universit\u00e4tsstra\u00dfe 150 44801 Bochum Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Philipp","family":"Gerschel","sequence":"additional","affiliation":[{"name":"Faculty of Chemistry & Biochemistry, Ruhr\u2010Universit\u00e4t Bochum, Universit\u00e4tsstra\u00dfe 150 44801 Bochum Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Dibya Jyoti","family":"Barman","sequence":"additional","affiliation":[{"name":"Institut f\u00fcr Chemie, Humboldt\u2010Universit\u00e4t zu Berlin Brook\u2010Taylor\u2010Str. 2 12489 Berlin Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Leon","family":"Gerndt","sequence":"additional","affiliation":[{"name":"Institut f\u00fcr Chemie, Humboldt\u2010Universit\u00e4t zu Berlin Brook\u2010Taylor\u2010Str. 2 12489 Berlin Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Thomas","family":"Lohmiller","sequence":"additional","affiliation":[{"name":"Institut f\u00fcr Chemie, Humboldt\u2010Universit\u00e4t zu Berlin Brook\u2010Taylor\u2010Str. 2 12489 Berlin Germany"},{"name":"EPR4Energy Joint Lab, Department Spins in Energy Conversion and Quantum Information Science Helmholtz Zentrum Berlin f\u00fcr Materialien und Energie GmbH Albert\u2010Einstein\u2010Stra\u00dfe 16 12489 Berlin Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Kaltum","family":"Abdiaziz","sequence":"additional","affiliation":[{"name":"Max Planck Institute for Chemical Energy Conversion 34\u201036 Stiftstra\u00dfe 45470 M\u00fclheim an der Ruhr Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Alexander","family":"Schnegg","sequence":"additional","affiliation":[{"name":"Max Planck Institute for Chemical Energy Conversion 34\u201036 Stiftstra\u00dfe 45470 M\u00fclheim an der Ruhr Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Maylis","family":"Orio","sequence":"additional","affiliation":[{"name":"Aix\u2010Marseille Univ, CNRS, Centrale Marseille iSm2 Marseille France"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Dennis G. 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