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However, susceptibility of these enzymes to oxygen\u2010induced degradation impedes their practical deployment in hydrogen\u2010production devices and fuel cells. Recent investigations into the oxygen\u2010stable (H<jats:sub>inact<\/jats:sub>) state of the H\u2010cluster revealed its inherent capacity to resist oxygen degradation. Herein, we present findings on Cl\u2010 and SH\u2010bound [2Fe\u20102S] complexes, bearing relevance to the oxygen\u2010stable state within a biological context. A characteristic attribute of these complexes is the terminal Cl<jats:sup>\u2212<\/jats:sup>\/SH<jats:sup>\u2212<\/jats:sup> ligation to the iron center bearing the CO bridge. Structural analysis of the t\u2010Cl demonstrates a striking resemblance to the H<jats:sub>inact<\/jats:sub> state of <jats:italic>Dd<\/jats:italic>HydAB and <jats:italic>Cb<\/jats:italic>A5H. The t\u2010Cl\/t\u2010SH exhibit reversible oxidation, with both redox species, electronically, being the first biomimetic analogs to the H<jats:sub>trans<\/jats:sub> and H<jats:sub>inact<\/jats:sub> states. These complexes exhibit notable resistance against oxygen\u2010induced decomposition, supporting the potential oxygen\u2010resistant nature of the H<jats:sub>trans<\/jats:sub> and H<jats:sub>inact<\/jats:sub> states. The swift reductive release of the Cl\u2010\/SH\u2010group demonstrates its labile and kinetically controlled binding. The findings garnered from these investigations offer valuable insights into properties of the enzymatic O<jats:sub>2<\/jats:sub>\u2010stable state, and key factors governing deactivation and reactivation conversion. This work contributes to the advancement of bio\u2010inspired molecular catalysts and the integration of enzymes and artificial catalysts into H<jats:sub>2<\/jats:sub>\u2010evolution devices and fuel\u2010cell applications.<\/jats:p>","DOI":"10.1002\/anie.202408142","type":"journal-article","created":{"date-parts":[[2024,5,31]],"date-time":"2024-05-31T08:10:07Z","timestamp":1717143007000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Chloride\u2010 and Hydrosulfide\u2010Bound 2Fe Complexes as Models of the Oxygen\u2010Stable State of [FeFe] Hydrogenase"],"prefix":"10.1002","volume":"63","author":[{"ORCID":"https:\/\/orcid.org\/0000-0001-6055-8039","authenticated-orcid":false,"given":"Yu\u2010Chiao","family":"Liu","sequence":"first","affiliation":[{"name":"Institute of Chemistry Academia Sinica, Nankang  Taipei 115 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