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While the original, starting aminopyridine <jats:bold>[(L<jats:sub>5<\/jats:sub><\/jats:bold><jats:sup><jats:bold>2<\/jats:bold><\/jats:sup><jats:bold>)Fe<jats:sup>II<\/jats:sup>(MeCN)](PF<jats:sub>6<\/jats:sub>)<\/jats:bold> complex is stable in air, the potentials of the new Fe<jats:sup>III\/II<\/jats:sup> couples decrease to the point that <jats:bold>[L<jats:sup>2<\/jats:sup>Fe<jats:sup>II<\/jats:sup>]<\/jats:bold> spontaneously reduces O<jats:sub>2<\/jats:sub> to superoxide. We used it as an O<jats:sub>2<\/jats:sub> activator in an electrochemical setup, as its presence allows to generate superoxide at a much more accessible potential (&gt;500\u2005mV gain). Our aim was to achieve substrate oxidation via the reductive activation of O<jats:sub>2<\/jats:sub>. While L<jats:sup>2<\/jats:sup>Fe<jats:sup>III<\/jats:sup>(OTf) proved to be a good O<jats:sub>2<\/jats:sub> activator but a poor oxidation system, its association with another complex (TPEN)Fe<jats:sup>II<\/jats:sup>(PF<jats:sub>6<\/jats:sub>)<jats:sub>2<\/jats:sub> generates a complementary tandem couple for electro\u2010assisted oxidation of substrates, working at a very accessible potential: upon reduction, L<jats:sup>2<\/jats:sup>Fe<jats:sup>III<\/jats:sup>(OTf) activates O<jats:sub>2<\/jats:sub> to superoxide and transfers it to (TPEN)Fe<jats:sup>II<\/jats:sup>(PF<jats:sub>6<\/jats:sub>)<jats:sub>2<\/jats:sub> leading <jats:italic>in fine<\/jats:italic> to the oxidation of thioanisole.<\/jats:p>","DOI":"10.1002\/chem.202200217","type":"journal-article","created":{"date-parts":[[2022,3,22]],"date-time":"2022-03-22T10:17:50Z","timestamp":1647944270000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":10,"title":["A Tale of Two Complexes: Electro\u2010Assisted Oxidation of Thioanisole by an \u201cO<sub>2<\/sub> Activator\/Oxidizing Species\u201d Tandem System of Non\u2010Heme Iron Complexes"],"prefix":"10.1002","volume":"28","author":[{"given":"Amanda Lyn","family":"Robinson","sequence":"first","affiliation":[{"name":"Institut de Chimie Mol\u00e9culaire et des Mat\u00e9riaux d'Orsay Universit\u00e9 Paris-Saclay  CNRS 91405 Orsay cedex France"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jean\u2010No\u00ebl","family":"Rebilly","sequence":"additional","affiliation":[{"name":"Institut de Chimie Mol\u00e9culaire et des Mat\u00e9riaux d'Orsay Universit\u00e9 Paris-Saclay  CNRS 91405 Orsay cedex France"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"R\u00e9gis","family":"Guillot","sequence":"additional","affiliation":[{"name":"Institut de Chimie Mol\u00e9culaire et des Mat\u00e9riaux d'Orsay Universit\u00e9 Paris-Saclay  CNRS 91405 Orsay cedex France"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Christian","family":"Herrero","sequence":"additional","affiliation":[{"name":"Institut de Chimie Mol\u00e9culaire et des Mat\u00e9riaux d'Orsay Universit\u00e9 Paris-Saclay  CNRS 91405 Orsay cedex France"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"H\u00e9l\u00e8ne","family":"Maisonneuve","sequence":"additional","affiliation":[{"name":"Institut de Chimie Mol\u00e9culaire et des Mat\u00e9riaux d'Orsay Universit\u00e9 Paris-Saclay  CNRS 91405 Orsay cedex France"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-8289-4965","authenticated-orcid":false,"given":"Fr\u00e9d\u00e9ric","family":"Banse","sequence":"additional","affiliation":[{"name":"Institut de Chimie Mol\u00e9culaire et des Mat\u00e9riaux d'Orsay Universit\u00e9 Paris-Saclay  CNRS 91405 Orsay cedex France"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2022,4,5]]},"reference":[{"key":"e_1_2_8_1_1","doi-asserted-by":"crossref","unstructured":"I. 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