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Despite many years of research there are still many questions related to its functioning. Thus, CDO is inactive with selenocysteine (Sec) or when the central iron ion is replaced by cobalt. In this context, we report here biomimetic CDO models with bound selenocysteamine substrate ligands, namely [Tp<jats:sup>Mes<\/jats:sup>Fe(Se\u2010CH<jats:sub>2<\/jats:sub>\u2010CH<jats:sub>2<\/jats:sub>\u2010NH<jats:sub>2<\/jats:sub>)] and [Tp<jats:sup>Mes*<\/jats:sup>Fe(Se\u2010CH<jats:sub>2<\/jats:sub>\u2010CH<jats:sub>2<\/jats:sub>\u2010NH<jats:sub>2<\/jats:sub>)] (with Tp<jats:sup>Mes<\/jats:sup>\u00a0=\u00a0hydrotris(3\u2010mesitylpyrazol\u20101\u2010yl)borate, Tp<jats:sup>Mes*<\/jats:sup> = hydrobis((3\u2010mesitylpyrazol\u20101\u2010yl)(5\u2010mesitylpyrazol\u20101\u2010yl)borate) and in addition a cobalt\u2010analogue [Tp<jats:sup>Mes<\/jats:sup>Co(Se\u2010CH<jats:sub>2<\/jats:sub>\u2010CH<jats:sub>2<\/jats:sub>\u2010NH<jats:sub>2<\/jats:sub>)]. Upon treatment of the Fe\/Se homologues with O<jats:sub>2<\/jats:sub> \u2013 as in case of the parent cysteamine\u2010bound complexes \u2013 the dioxygenation of the chalcogen atoms was observed. This suggests that the lack in reactivity of CDO\u2010Sec toward O<jats:sub>2<\/jats:sub> does not originate in the electronic situation but in the surrounding protein matrix. Subsequent DFT calculations indeed showed lower initial barriers for selenocysteamine than for cysteamine in support of the experimental work. The complex [Tp<jats:sup>Mes<\/jats:sup>Co(Se\u2010CH<jats:sub>2<\/jats:sub>\u2010CH<jats:sub>2<\/jats:sub>\u2010NH<jats:sub>2<\/jats:sub>)], where Fe is formally replaced by Co, also reacts with dioxygen \u2013 more slowly but selectively \u2013 to give [Tp<jats:sup>Mes<\/jats:sup>Co(O<jats:sub>2<\/jats:sub>Se\u2010CH<jats:sub>2<\/jats:sub>\u2010CH<jats:sub>2<\/jats:sub>\u2010NH<jats:sub>2<\/jats:sub>)]. Hence, this is an experimental observation of a dioxygenation with O<jats:sub>2<\/jats:sub> mediated by a cobalt center in a molecular compound, which is so far without precedence.<\/jats:p>","DOI":"10.1002\/anie.202507578","type":"journal-article","created":{"date-parts":[[2025,8,19]],"date-time":"2025-08-19T11:07:19Z","timestamp":1755601639000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":3,"title":["Promiscuity in Molecular Mimics of the Cysteine Dioxygenase: Effects of Selenium in the Substrate and Cobalt as the Central Metal Ion"],"prefix":"10.1002","volume":"64","author":[{"given":"Kilian","family":"Wei\u00dfer","sequence":"first","affiliation":[{"name":"Institut f\u00fcr Chemie Humboldt\u2010Universit\u00e4t zu Berlin  Brook\u2010Taylor Stra\u00dfe 2 12489 Berlin Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Edgar T. K.","family":"Weber","sequence":"additional","affiliation":[{"name":"Institut f\u00fcr Chemie Humboldt\u2010Universit\u00e4t zu Berlin  Brook\u2010Taylor Stra\u00dfe 2 12489 Berlin Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Gunasekaran","family":"Velmurugan","sequence":"additional","affiliation":[{"name":"Institut f\u00fcr Anorganische Chemie and Interdisciplinary Center for Scientific Computing (IWR) Universit\u00e4t Heidelberg  Im Neuenheimer Feld 270 69120 Heidelberg 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 Stra\u00dfe 2 12489 Berlin Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Konstantin B.","family":"Krause","sequence":"additional","affiliation":[{"name":"Institut f\u00fcr Chemie Humboldt\u2010Universit\u00e4t zu Berlin  Brook\u2010Taylor Stra\u00dfe 2 12489 Berlin Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-7927-8002","authenticated-orcid":false,"given":"Siad","family":"Wolff","sequence":"additional","affiliation":[{"name":"Institut f\u00fcr Chemie Humboldt\u2010Universit\u00e4t zu Berlin  Brook\u2010Taylor Stra\u00dfe 2 12489 Berlin Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"M. 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