{"id":1522,"date":"2025-12-23T13:13:16","date_gmt":"2025-12-23T13:13:16","guid":{"rendered":"https:\/\/citations.tools.bio-logic.fr\/?p=1522"},"modified":"2025-12-23T13:13:16","modified_gmt":"2025-12-23T13:13:16","slug":"electrochemical-water-oxidation-and-stereoselective-oxygen-atom-transfer-mediated-by-a-copper-complex","status":"publish","type":"post","link":"https:\/\/citations.tools.bio-logic.fr\/?p=1522","title":{"rendered":"Electrochemical Water Oxidation and Stereoselective Oxygen Atom Transfer Mediated by a Copper Complex"},"content":{"rendered":"<h4>DOI:<\/h4>\n<p><a href=\"https:\/\/doi.org\/10.1002\/chem.201704613\" target=\"_blank\" rel=\"noopener\">10.1002\/chem.201704613<\/a><\/p>\n<h4>Authors:<\/h4>\n<p>Maria-Chrysanthi Kafentzi, Raffaello Papadakis, Federica Gennarini, Am\u00e9lie Kochem, Olga Iranzo, Yves Le Mest, Nicolas Le Poul, Thierry Tron, Bruno Faure, A. Jalila Simaan, Marius R\u00e9glier<\/p>\n<h4>Abstract:<\/h4>\n<p>Abstract Water oxidation by copper\u2010based complexes to form dioxygen has attracted attention in recent years, with the aim of developing efficient and cheap catalysts for chemical energy storage. In addition, high\u2010valent metal\u2013oxo species produced by the oxidation of metal complexes in the presence of water can be used to achieve substrate oxygenation with the use of H 2 O as an oxygen source. To date, this strategy has not been reported for copper complexes. Herein, a copper(II) complex, [(RPY2)Cu(OTf) 2 ] (RPY2=N\u2010substituted bis[2\u2010pyridyl(ethylamine)] ligands; R=indane; OTf=triflate), is used. This complex, which contains an oxidizable substrate moiety (indane), is used as a tool to monitor an intramolecular oxygen atom transfer reaction. Electrochemical properties were investigated and, upon electrolysis at 1.30 V versus a normal hydrogen electrode (NHE), both dioxygen production and oxygenation of the indane moiety were observed. The ligand was oxidized in a highly diastereoselective manner, which indicated that the observed reactivity was mediated by metal\u2010centered reactive species. The pH dependence of the reactivity was monitored and correlated with speciation deduced from different techniques, ranging from potentiometric titrations to spectroscopic studies and DFT calculations. Water oxidation for dioxygen production occurs at neutral pH and is probably mediated by the oxidation of a mononuclear copper(II) precursor. It is achieved with a rather low overpotential (280 mV at pH 7), although with limited efficiency. On the other hand, oxygenation is maximum at pH 8\u20138.5 and is probably mediated by the electrochemical oxidation of an antiferromagnetically coupled dinuclear bis(\u03bc\u2010hydroxo) copper(II) precursor. This constitutes the first example of copper\u2010centered oxidative water activation for a selective oxygenation reaction.<\/p>\n","protected":false},"excerpt":{"rendered":"<h4>DOI:<\/h4>\n<div class=\"b-doi\">10.1002\/chem.201704613<\/div>\n<h4>Authors:<\/h4>\n<div class=\"b-author\">Maria-Chrysanthi Kafentzi, Raffaello Papadakis, Federica Gennarini, Am\u00e9lie Kochem, Olga Iranzo, Yves Le Mest, Nicolas Le Poul, Thierry Tron, Bruno Faure, A. Jalila Simaan, Marius R\u00e9glier<\/div>\n<h4>Abstract:<\/h4>\n<div class=\"b-intro\">Abstract Water oxidation by copper\u2010based complexes to form dioxygen has attracted attention in recent years, with the aim of developing efficient and cheap catalysts for chemical energy storage. In addition, high\u2010valent metal\u2013oxo species produced by the oxidation of metal complexes in the presence of water can be used to achieve&hellip;<\/div>\n","protected":false},"author":1,"featured_media":0,"comment_status":"open","ping_status":"open","sticky":false,"template":"","format":"standard","meta":{"footnotes":""},"categories":[25],"tags":[],"class_list":["post-1522","post","type-post","status-publish","format-standard","hentry","category-sp-150-potentiostat"],"_links":{"self":[{"href":"https:\/\/citations.tools.bio-logic.fr\/index.php?rest_route=\/wp\/v2\/posts\/1522","targetHints":{"allow":["GET"]}}],"collection":[{"href":"https:\/\/citations.tools.bio-logic.fr\/index.php?rest_route=\/wp\/v2\/posts"}],"about":[{"href":"https:\/\/citations.tools.bio-logic.fr\/index.php?rest_route=\/wp\/v2\/types\/post"}],"author":[{"embeddable":true,"href":"https:\/\/citations.tools.bio-logic.fr\/index.php?rest_route=\/wp\/v2\/users\/1"}],"replies":[{"embeddable":true,"href":"https:\/\/citations.tools.bio-logic.fr\/index.php?rest_route=%2Fwp%2Fv2%2Fcomments&post=1522"}],"version-history":[{"count":0,"href":"https:\/\/citations.tools.bio-logic.fr\/index.php?rest_route=\/wp\/v2\/posts\/1522\/revisions"}],"wp:attachment":[{"href":"https:\/\/citations.tools.bio-logic.fr\/index.php?rest_route=%2Fwp%2Fv2%2Fmedia&parent=1522"}],"wp:term":[{"taxonomy":"category","embeddable":true,"href":"https:\/\/citations.tools.bio-logic.fr\/index.php?rest_route=%2Fwp%2Fv2%2Fcategories&post=1522"},{"taxonomy":"post_tag","embeddable":true,"href":"https:\/\/citations.tools.bio-logic.fr\/index.php?rest_route=%2Fwp%2Fv2%2Ftags&post=1522"}],"curies":[{"name":"wp","href":"https:\/\/api.w.org\/{rel}","templated":true}]}}