{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,2,4]],"date-time":"2026-02-04T20:10:09Z","timestamp":1770235809567,"version":"3.49.0"},"reference-count":40,"publisher":"Wiley","issue":"72","license":[{"start":{"date-parts":[[2017,11,30]],"date-time":"2017-11-30T00:00:00Z","timestamp":1512000000000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"funder":[{"DOI":"10.13039\/100000002","name":"National Institutes of Health","doi-asserted-by":"publisher","award":["GM028962"],"award-info":[{"award-number":["GM028962"]}],"id":[{"id":"10.13039\/100000002","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Chemistry A European J"],"published-print":{"date-parts":[[2017,12,22]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>Direct experimental determination of redox properties of superoxo (O<jats:sub>2<\/jats:sub><jats:sup>.\u2212<\/jats:sup>) and peroxo (O<jats:sub>2<\/jats:sub><jats:sup>2\u2212<\/jats:sup>) embedded in dicopper complexes bearing an unsymmetrical binucleating ligand was achieved using cryo\u2010electrochemistry and cryo\u2010spectroelectrochemistry in dichloromethane. Cyclic voltammetry for dicopper(I) (<jats:bold>1<jats:sup>+<\/jats:sup><\/jats:bold>) oxidation to a Cu<jats:sup>I<\/jats:sup>Cu<jats:sup>II<\/jats:sup> mixed\u2010valent species (<jats:bold>1<jats:sup>2+<\/jats:sup><\/jats:bold>) under inert atmosphere at 193\u2005K reveals slow heterogeneous electron\u2010transfer kinetics, indicative of a large reorganization energy. Oxygenation of the dicuprous complex\u2005<jats:bold>1<jats:sup>+<\/jats:sup><\/jats:bold> gives the bridged peroxo dicopper(II) species\u2005<jats:bold>3<jats:sup>+<\/jats:sup><\/jats:bold>, which is reversibly oxidized to the superoxo complex\u2005<jats:bold>2<jats:sup>2+<\/jats:sup><\/jats:bold> at <jats:italic>E<\/jats:italic><jats:sup>0<\/jats:sup>=0.11\u2005V (vs. SCE) with a small inner sphere electron\u2010transfer reorganization energy, <jats:italic>\u03bb<\/jats:italic><jats:sub>i<\/jats:sub>=0.54\u2005eV, determined from variable temperature electrochemical impedance spectroscopy. The data suggest that the O<jats:sub>2<\/jats:sub><jats:sup>.\u2212<\/jats:sup>\/O<jats:sub>2<\/jats:sub><jats:sup>2\u2212<\/jats:sup> redox process occurs directly on the O<jats:sub>2<\/jats:sub>\u2010derived core.<\/jats:p>","DOI":"10.1002\/chem.201705066","type":"journal-article","created":{"date-parts":[[2017,10,26]],"date-time":"2017-10-26T13:32:39Z","timestamp":1509024759000},"page":"18314-18319","source":"Crossref","is-referenced-by-count":14,"title":["Direct Determination of Electron\u2010Transfer Properties of Dicopper\u2010Bound Reduced Dioxygen Species by a Cryo\u2010Spectroelectrochemical Approach."],"prefix":"10.1002","volume":"23","author":[{"given":"Isidoro","family":"L\u00f3pez","sequence":"first","affiliation":[{"name":"UMR CNRS 6521 Universit\u00e9 de Bretagne Occidentale  6 Avenue Le Gorgeu CS 93837 29238 Brest Cedex 3 France"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Rui","family":"Cao","sequence":"additional","affiliation":[{"name":"Department of Chemistry Johns Hopkins University  Baltimore Maryland 21218 USA"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"David A.","family":"Quist","sequence":"additional","affiliation":[{"name":"Department of Chemistry Johns Hopkins University  Baltimore Maryland 21218 USA"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5675-7040","authenticated-orcid":false,"given":"Kenneth D.","family":"Karlin","sequence":"additional","affiliation":[{"name":"Department of Chemistry Johns Hopkins University  Baltimore Maryland 21218 USA"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5915-3760","authenticated-orcid":false,"given":"Nicolas","family":"Le\u2005Poul","sequence":"additional","affiliation":[{"name":"UMR CNRS 6521 Universit\u00e9 de Bretagne Occidentale  6 Avenue Le Gorgeu CS 93837 29238 Brest Cedex 3 France"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2017,11,30]]},"reference":[{"key":"e_1_2_2_1_1","unstructured":"\u00a0"},{"key":"e_1_2_2_2_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr400327t"},{"key":"e_1_2_2_3_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr4005296"},{"key":"e_1_2_2_4_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr400415k"},{"key":"e_1_2_2_5_1","doi-asserted-by":"publisher","DOI":"10.1126\/science.1094583"},{"key":"e_1_2_2_6_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.biochem.7b00019"},{"key":"e_1_2_2_7_1","doi-asserted-by":"publisher","DOI":"10.1002\/prot.340190405"},{"key":"e_1_2_2_8_1","doi-asserted-by":"publisher","DOI":"10.1074\/jbc.M509785200"},{"key":"e_1_2_2_9_1","doi-asserted-by":"publisher","DOI":"10.1073\/pnas.0906095106"},{"key":"e_1_2_2_10_1","unstructured":"Synthetic model system crystal structures exist for peroxo-CuII2 superoxo-CuII peroxo-CuIII and CuIII2(\u03bc-O)2complexes. See refs.\u2005[1a] and [9]."},{"key":"e_1_2_2_11_1","unstructured":"There are a number of X-ray structures for multicopper (four ions) oxidases containing a reduced dioxygen species surrounded by three Cu ions; there may be issues surrounding the interpretation of X-ray data due to radiation damage. 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