{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,8,17]],"date-time":"2026-08-17T14:31:39Z","timestamp":1786977099019,"version":"build-2736575974"},"reference-count":47,"publisher":"Wiley","issue":"11","license":[{"start":{"date-parts":[[2025,4,30]],"date-time":"2025-04-30T00:00:00Z","timestamp":1745971200000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/creativecommons.org\/licenses\/by\/4.0\/"},{"start":{"date-parts":[[2025,4,30]],"date-time":"2025-04-30T00:00:00Z","timestamp":1745971200000},"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":["EXC 2008\u2013390540038"],"award-info":[{"award-number":["EXC 2008\u2013390540038"]}],"id":[{"id":"10.13039\/501100001659","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["aces.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Chemistry \u0097 An Asian Journal"],"published-print":{"date-parts":[[2025,6]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>\n                    A dinuclear copper(I) complex\n                    <jats:bold>\n                      Cu\n                      <jats:sub>2<\/jats:sub>\n                      L2\n                      <jats:sub>2<\/jats:sub>\n                    <\/jats:bold>\n                    (\n                    <jats:bold>L2\u00a0<\/jats:bold>\n                    =\u00a03,3\u2010dimethyl\u20101\u2010(1\u2010methyl\u20101\n                    <jats:italic>H<\/jats:italic>\n                    \u2010benzo[\n                    <jats:italic>d<\/jats:italic>\n                    ]imidazole\u20102\u2010yl)\u2010\n                    <jats:italic>N<\/jats:italic>\n                    \u2010(propan\u20102\u2010ylidene)butan\u20102\u2010amine) containing benzimidazole and imino donors was previously reported by some of us as an efficient catalyst for the aerobic oxidation of alcohols to aldehydes in presence of TEMPO (2,2,6,6\u2010tetramethylpiperidinyloxyl) and an external base NMI (\n                    <jats:italic>N<\/jats:italic>\n                    \u2010methyl imidazole). Cu(III)\n                    <jats:sub>2<\/jats:sub>\n                    (bis\u2010\n                    <jats:italic>\u03bc<\/jats:italic>\n                    \u2010oxo) and Cu(II)\n                    <jats:sub>2<\/jats:sub>\n                    (bis\u2010\n                    <jats:italic>\u03bc<\/jats:italic>\n                    \u2010hydroxo) cores were trapped as viable intermediates in the reaction, which provided deeper mechanistic insights. Here, we report two new ligand systems\n                    <jats:bold>L3<\/jats:bold>\n                    (\n                    <jats:italic>N<\/jats:italic>\n                    \u2010isopropyl\u20103,3\u2010dimethyl\u20101\u2010(1\u2010methyl\u20101\n                    <jats:italic>H<\/jats:italic>\n                    \u2010benzol[\n                    <jats:italic>d<\/jats:italic>\n                    ]imidazole\u20102\u2010yl)butane\u20102\u2010amine) and\n                    <jats:bold>L4<\/jats:bold>\n                    ((\n                    <jats:italic>Z<\/jats:italic>\n                    )\u20102,4\u2010di\u2010\n                    <jats:italic>tert<\/jats:italic>\n                    \u2010butyl\u20106\u2010(((3,3\u2010dimethyl\u20101\u2010(1\u2010methyl\u20101\n                    <jats:italic>H<\/jats:italic>\n                    \u2010benzol[\n                    <jats:italic>d<\/jats:italic>\n                    ]imidazole\u20102\u2010yl)butane\u20102\u2010yl)imino)methyl)phenol), which are designed to perturb the overall electronics of the complexes and the resulting effects on their O\n                    <jats:sub>2<\/jats:sub>\n                    activation mechanisms. The stronger donation of the secondary amine group stabilizes a mononuclear\n                    <jats:bold>\n                      Cu\n                      <jats:sup>I<\/jats:sup>\n                      L3\n                    <\/jats:bold>\n                    core, which nevertheless follows a dinuclear O\n                    <jats:sub>2<\/jats:sub>\n                    activation mechanism as in\n                    <jats:bold>\n                      Cu\n                      <jats:sub>2<\/jats:sub>\n                      L2\n                      <jats:sub>2<\/jats:sub>\n                    <\/jats:bold>\n                    . Notably, the\n                    <jats:bold>\n                      Cu\n                      <jats:sup>I<\/jats:sup>\n                      L3\n                    <\/jats:bold>\n                    \/TEMPO catalyst system performs the aerobic oxidation of alcohols to aldehydes with good yields and turnover numbers, even in the absence of NMI. The dinuclear\n                    <jats:bold>\n                      Cu\n                      <jats:sup>I<\/jats:sup>\n                      <jats:sub>2<\/jats:sub>\n                      L4\n                      <jats:sub>2<\/jats:sub>\n                    <\/jats:bold>\n                    complex involving a non\u2010innocent phenolate group, in contrast, exhibits depleted catalytic activity, because of the instability of the Cu(III)\n                    <jats:sub>2<\/jats:sub>\n                    (bis\u2010\n                    <jats:italic>\u03bc<\/jats:italic>\n                    \u2010oxo) core against intramolecular H\u2010atom abstraction to form an alkoxo bridged dicopper(II) complex.\n                  <\/jats:p>","DOI":"10.1002\/asia.202500123","type":"journal-article","created":{"date-parts":[[2025,4,30]],"date-time":"2025-04-30T20:23:08Z","timestamp":1746044588000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":1,"title":["Tuning Reactivity in Cu\/TEMPO Catalyzed Alcohol Oxidation Reactions"],"prefix":"10.1002","volume":"20","author":[{"given":"Maximilian","family":"Sch\u00fctze","sequence":"first","affiliation":[{"name":"Institut f\u00fcr Chemie Humboldt\u2010Universit\u00e4t zu Berlin  Brook\u2010Taylor\u2010Stra\u00dfe 2 Berlin 12489 Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Matthias","family":"Jux","sequence":"additional","affiliation":[{"name":"Institut f\u00fcr Chemie Humboldt\u2010Universit\u00e4t zu Berlin  Brook\u2010Taylor\u2010Stra\u00dfe 2 Berlin 12489 Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Beatrice","family":"Cula","sequence":"additional","affiliation":[{"name":"Institut f\u00fcr Chemie Humboldt\u2010Universit\u00e4t zu Berlin  Brook\u2010Taylor\u2010Stra\u00dfe 2 Berlin 12489 Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Michael","family":"Haumann","sequence":"additional","affiliation":[{"name":"Fachbereich Physik Freie Universit\u00e4t Berlin  Arnimallee 14 Berlin 14195 Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Sagie","family":"Katz","sequence":"additional","affiliation":[{"name":"Institut f\u00fcr Chemie Fakult\u00e4t II Technische Universit\u00e4t Berlin  Stra\u00dfe des 17. Juni 135 Berlin 10623 Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Peter","family":"Hildebrandt","sequence":"additional","affiliation":[{"name":"Institut f\u00fcr Chemie Fakult\u00e4t II Technische Universit\u00e4t Berlin  Stra\u00dfe des 17. Juni 135 Berlin 10623 Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Holger","family":"Dau","sequence":"additional","affiliation":[{"name":"Fachbereich Physik Freie Universit\u00e4t Berlin  Arnimallee 14 Berlin 14195 Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Kallol","family":"Ray","sequence":"additional","affiliation":[{"name":"Institut f\u00fcr Chemie Humboldt\u2010Universit\u00e4t zu Berlin  Brook\u2010Taylor\u2010Stra\u00dfe 2 Berlin 12489 Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2025,4,30]]},"reference":[{"key":"e_1_2_8_1_1","doi-asserted-by":"publisher","DOI":"10.1007\/s00775-016-1415-2"},{"key":"e_1_2_8_1_2","doi-asserted-by":"publisher","DOI":"10.1021\/acsomega.2c04432"},{"key":"e_1_2_8_1_3","doi-asserted-by":"publisher","DOI":"10.1038\/s41929-021-00591-4"},{"key":"e_1_2_8_1_4","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.1c04082"},{"key":"e_1_2_8_1_5","doi-asserted-by":"publisher","DOI":"10.1021\/acs.inorgchem.6b02165"},{"key":"e_1_2_8_1_6","doi-asserted-by":"publisher","DOI":"10.1002\/ejic.202300774"},{"key":"e_1_2_8_2_1","doi-asserted-by":"publisher","DOI":"10.1039\/D2CC06990C"},{"key":"e_1_2_8_2_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.6b00636"},{"key":"e_1_2_8_2_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202101035"},{"key":"e_1_2_8_2_4","doi-asserted-by":"publisher","DOI":"10.1126\/science.aav2572"},{"key":"e_1_2_8_2_5","doi-asserted-by":"publisher","DOI":"10.1021\/acs.accounts.5b00220"},{"key":"e_1_2_8_3_1","doi-asserted-by":"publisher","DOI":"10.1002\/cplu.201600636"},{"key":"e_1_2_8_3_2","doi-asserted-by":"publisher","DOI":"10.1038\/s41929-018-0110-9"},{"key":"e_1_2_8_3_3","doi-asserted-by":"publisher","DOI":"10.1039\/D0CC01392G"},{"key":"e_1_2_8_3_4","doi-asserted-by":"publisher","DOI":"10.1016\/j.jinorgbio.2021.111557"},{"key":"e_1_2_8_4_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.inorgchem.4c03304"},{"key":"e_1_2_8_4_2","doi-asserted-by":"publisher","DOI":"10.1002\/cctc.202300933"},{"key":"e_1_2_8_4_3","doi-asserted-by":"publisher","DOI":"10.1126\/science.279.5350.537"},{"key":"e_1_2_8_5_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr020632z"},{"key":"e_1_2_8_5_2","doi-asserted-by":"publisher","DOI":"10.1007\/s00775-016-1420-5"},{"key":"e_1_2_8_5_3","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3773(20020402)41:7<1114::AID-ANIE1114>3.0.CO;2-6"},{"key":"e_1_2_8_5_4","doi-asserted-by":"publisher","DOI":"10.1002\/asia.202100286"},{"key":"e_1_2_8_5_5","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201000973"},{"key":"e_1_2_8_5_6","doi-asserted-by":"publisher","DOI":"10.1039\/D4SC01762E"},{"key":"e_1_2_8_5_7","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201600551"},{"key":"e_1_2_8_6_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202108442"},{"key":"e_1_2_8_7_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.8b08748"},{"key":"e_1_2_8_7_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.mcat.2021.111637"},{"key":"e_1_2_8_7_3","doi-asserted-by":"publisher","DOI":"10.1016\/j.mcat.2022.112167"},{"key":"e_1_2_8_7_4","doi-asserted-by":"publisher","DOI":"10.1021\/ja206230h"},{"key":"e_1_2_8_7_5","doi-asserted-by":"publisher","DOI":"10.1021\/ja3117203"},{"key":"e_1_2_8_8_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.0c03867"},{"key":"e_1_2_8_8_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.accounts.5b00169"},{"key":"e_1_2_8_8_3","doi-asserted-by":"publisher","DOI":"10.1021\/ja207882h"},{"key":"e_1_2_8_9_1","unstructured":"Deposition numbers 2411973 (for 3\u2010amino\u20104 4\u2010dimethylpentanoic acid \u00d7 H2O) 2411974 (for L1) 2411975 (for L2) 2411976 (for L3) 2411977 (for L4) 2388744 (for CuIL3) 2411978 (for CuI2L42) 2411979 (for CuII2O\u2010L42\u00d7 2 C2H3N)2and 2411980 (for CuII2O\u2010L42\u00d7 C2H3N \u00d7 C7H8O2) contain the supplementary crystallographic data for this paper. These data are provided free of charge by the joint Cambridge Crystallographic Data Centre and Fachinformationszentrum Karlsruhe Access Structures service."},{"key":"e_1_2_8_10_1","doi-asserted-by":"publisher","DOI":"10.1007\/s00775-002-0420-9"},{"key":"e_1_2_8_10_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic00225a001"},{"key":"e_1_2_8_11_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja9918425"},{"key":"e_1_2_8_11_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja972946n"},{"key":"e_1_2_8_11_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201402166"},{"key":"e_1_2_8_12_1","unstructured":"G. M.Sheldrick SADABS University of G\u00f6ttingen Germany 1996."},{"key":"e_1_2_8_13_1","doi-asserted-by":"publisher","DOI":"10.1107\/S2053273314026370"},{"key":"e_1_2_8_14_1","first-page":"3","volume":"71","author":"Sheldrick G.","year":"2015","journal-title":"Acta Crys. Sec. C"},{"key":"e_1_2_8_15_1","doi-asserted-by":"publisher","DOI":"10.1107\/S0021889811043202"},{"key":"e_1_2_8_16_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.jmr.2005.08.013"},{"key":"e_1_2_8_17_1","doi-asserted-by":"publisher","DOI":"10.1007\/s00216-003-1982-2"},{"key":"e_1_2_8_18_1","doi-asserted-by":"publisher","DOI":"10.1039\/b926434e"}],"container-title":["Chemistry \u2013 An Asian Journal"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/aces.onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/asia.202500123","content-type":"application\/pdf","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/aces.onlinelibrary.wiley.com\/doi\/full-xml\/10.1002\/asia.202500123","content-type":"application\/xml","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/aces.onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/asia.202500123","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,2,12]],"date-time":"2026-02-12T15:59:46Z","timestamp":1770911986000},"score":1,"resource":{"primary":{"URL":"https:\/\/aces.onlinelibrary.wiley.com\/doi\/10.1002\/asia.202500123"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2025,4,30]]},"references-count":47,"journal-issue":{"issue":"11","published-print":{"date-parts":[[2025,6]]}},"alternative-id":["10.1002\/asia.202500123"],"URL":"https:\/\/doi.org\/10.1002\/asia.202500123","archive":["Portico"],"relation":{},"ISSN":["1861-4728","1861-471X"],"issn-type":[{"value":"1861-4728","type":"print"},{"value":"1861-471X","type":"electronic"}],"subject":[],"published":{"date-parts":[[2025,4,30]]},"assertion":[{"value":"2025-01-26","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2025-04-03","order":2,"name":"accepted","label":"Accepted","group":{"name":"publication_history","label":"Publication History"}},{"value":"2025-04-30","order":3,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}],"article-number":"e202500123"}}