{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,11,3]],"date-time":"2026-11-03T15:31:28Z","timestamp":1793719888109,"version":"4.6.1"},"reference-count":50,"publisher":"Wiley","issue":"41","license":[{"start":{"date-parts":[[2026,8,14]],"date-time":"2026-08-14T00:00:00Z","timestamp":1786665600000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/creativecommons.org\/licenses\/by\/4.0\/"},{"start":{"date-parts":[[2026,8,14]],"date-time":"2026-08-14T00:00:00Z","timestamp":1786665600000},"content-version":"tdm","delay-in-days":0,"URL":"http:\/\/doi.wiley.com\/10.1002\/tdm_license_1.1"}],"funder":[{"DOI":"10.13039\/501100001659","name":"Deutsche Forschungsgemeinschaft","doi-asserted-by":"publisher","award":["4058109"],"award-info":[{"award-number":["4058109"]}],"id":[{"id":"10.13039\/501100001659","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["chemistry-europe.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Chemistry A European J"],"published-print":{"date-parts":[[2026,11,3]]},"abstract":"ABSTRACT<\/jats:title>\n \n Cu\n I<\/jats:sup>\n (14 TMCO) (\n 1<\/jats:bold>\n ), involving a N\n 3<\/jats:sub>\n O\u2010macrocycle, reacts with O\n 2<\/jats:sub>\n at cryogenic temperatures to yield an\n end\u2010on<\/jats:italic>\n peroxodicopper(II) species. The N\n 4<\/jats:sub>\n \u2010analogue Cu\n I<\/jats:sup>\n (14\u2010TMC) (\n 2<\/jats:bold>\n ) remains unreactive under similar conditions.\n 2<\/jats:bold>\n contains an average short Cu\u2500N bond length, resulting in a dominating\n trans<\/jats:italic>\n \u2010effect, which inhibits O\n 2<\/jats:sub>\n binding. In contrast, an elongated Cu\u2500O\n TMCO<\/jats:sub>\n bond\n trans<\/jats:italic>\n to the O\n 2<\/jats:sub>\n \u2010binding site in\n 1<\/jats:bold>\n allows O\n 2<\/jats:sub>\n \u2010coordination. The catalytic reduction of O\n 2<\/jats:sub>\n to H\n 2<\/jats:sub>\n O undergoes a full 4e\n \u2212<\/jats:sup>\n \/4H\n +<\/jats:sup>\n process in\n 1<\/jats:bold>\n . Notably, [Cu\n I<\/jats:sup>\n (12\u2010TMC)]\n +<\/jats:sup>\n (\n 3<\/jats:bold>\n ), involving a smaller N\n 4<\/jats:sub>\n \u2010macrocycle where the Cu(I) ion is forced to move out of the plane formed by the four nitrogen atoms, also binds O\n 2<\/jats:sub>\n . However, in contrast to\n 1<\/jats:bold>\n ,\n 3<\/jats:bold>\n mediates the catalytic 2e\n \u2212<\/jats:sup>\n \/2H\n +<\/jats:sup>\n reduction of O\n 2<\/jats:sub>\n to H\n 2<\/jats:sub>\n O\n 2<\/jats:sub>\n via two ligand\u2010assisted protonation steps. In this case, the reduction of O\n 2<\/jats:sub>\n involves the initial formation of a\n side\u2010on<\/jats:italic>\n peroxodicopper(II) species, where the weak Cu\u2500O\n peroxo<\/jats:sub>\n bond distance resulting from the strong \u03c3\u2010donation from the\n trans<\/jats:italic>\n Cu\u2500N bond presumably leads to the release of H\n 2<\/jats:sub>\n O\n 2<\/jats:sub>\n upon protonation. The present study provides deep mechanistic insights into the transition metal\u2010mediated O\n 2<\/jats:sub>\n reduction process and reveals how the first coordination sphere can be tuned to control the 2e\n \u2212<\/jats:sup>\n \/2H\n +<\/jats:sup>\n versus 4e\n \u2212<\/jats:sup>\n \/4H\n +<\/jats:sup>\n reductions of O\n 2<\/jats:sub>\n .\n <\/jats:p>","DOI":"10.1002\/chem.71479","type":"journal-article","created":{"date-parts":[[2026,8,14]],"date-time":"2026-08-14T12:36:25Z","timestamp":1786710985000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Dioxygen Reduction at a Cu(I) Complex Supported by a Macrocyclic N\n 3<\/sub>\n O Ligand System"],"prefix":"10.1002","volume":"32","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-4053-2525","authenticated-orcid":false,"given":"Maximilian","family":"Sch\u00fctze","sequence":"first","affiliation":[{"name":"Humboldt\u2010Universit\u00e4t Zu Berlin Institut F\u00fcr Chemie Berlin Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-3900-5362","authenticated-orcid":false,"given":"Dibya Jyoti","family":"Barman","sequence":"additional","affiliation":[{"name":"Humboldt\u2010Universit\u00e4t Zu Berlin Institut F\u00fcr Chemie Berlin Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9057-4523","authenticated-orcid":false,"given":"Christian","family":"Lorent","sequence":"additional","affiliation":[{"name":"Technische Universit\u00e4t Institut F\u00fcr Chemie Fakult\u00e4t II Berlin Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-2074-8844","authenticated-orcid":false,"given":"Kallol","family":"Ray","sequence":"additional","affiliation":[{"name":"Humboldt\u2010Universit\u00e4t Zu Berlin Institut F\u00fcr Chemie Berlin 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