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Despite many efforts, intermediates that would provide insight into how the non\u2010heme diiron active sites of FNORs reduce NO to N\n                    <jats:sub>2<\/jats:sub>\n                    O could not be identified. Computations predict that iron\u2010hyponitrite complexes are the key species, leading from NO to N\n                    <jats:sub>2<\/jats:sub>\n                    O. However, the coordination chemistry of non\u2010heme iron centers with hyponitrite is largely unknown. In this study, we report the reactivity of two non\u2010heme iron complexes with preformed hyponitrite. In the case of [Fe(TPA)(CH\n                    <jats:sub>3<\/jats:sub>\n                    CN)\n                    <jats:sub>2<\/jats:sub>\n                    ](OTf)\n                    <jats:sub>2<\/jats:sub>\n                    , cleavage of hyponitrite and formation of an Fe\n                    <jats:sub>2<\/jats:sub>\n                    (NO)\n                    <jats:sub>2<\/jats:sub>\n                    diamond core is observed. With less Lewis\u2010acidic [Fe\n                    <jats:sub>2<\/jats:sub>\n                    (BMPA\u2010PhO)\n                    <jats:sub>2<\/jats:sub>\n                    (OTf)\n                    <jats:sub>2<\/jats:sub>\n                    ] (\n                    <jats:bold>2<\/jats:bold>\n                    ), reaction with Na\n                    <jats:sub>2<\/jats:sub>\n                    N\n                    <jats:sub>2<\/jats:sub>\n                    O\n                    <jats:sub>2<\/jats:sub>\n                    in polar aprotic solvent leads to the formation of a red complex,\n                    <jats:bold>3<\/jats:bold>\n                    . X\u2010ray crystallography shows that\n                    <jats:bold>3<\/jats:bold>\n                    is a tetranuclear iron\u2010hyponitrite complex, [{Fe\n                    <jats:sub>2<\/jats:sub>\n                    (BMPA\u2010PhO)\n                    <jats:sub>2<\/jats:sub>\n                    }\n                    <jats:sub>2<\/jats:sub>\n                    (\u03bc\u2010N\n                    <jats:sub>2<\/jats:sub>\n                    O\n                    <jats:sub>2<\/jats:sub>\n                    )](OTf)\n                    <jats:sub>2<\/jats:sub>\n                    , with a unique hyponitrite binding mode. This species provided the unique opportunity to us to study the interaction of hyponitrite with non\u2010heme iron centers and the reactivity of the bound hyponitrite ligand. Here, either protonation or oxidation of\n                    <jats:bold>3<\/jats:bold>\n                    is found to induce N\n                    <jats:sub>2<\/jats:sub>\n                    O formation, supporting the hypothesis that hyponitrite is a viable intermediate in NO reduction.\n                  <\/jats:p>","DOI":"10.1002\/anie.202409700","type":"journal-article","created":{"date-parts":[[2024,9,10]],"date-time":"2024-09-10T11:09:19Z","timestamp":1725966559000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":4,"title":["Synthesis and Structural Characterization of a Non\u2010Heme Iron Hyponitrite Complex"],"prefix":"10.1002","volume":"63","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-1003-4357","authenticated-orcid":false,"given":"Michael O.","family":"Lengel","sequence":"first","affiliation":[{"name":"Department of Chemistry The University of Michigan  Ann Arbor Michigan 48109-1055"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Hai T.","family":"Dong","sequence":"additional","affiliation":[{"name":"Department of Chemistry The University of Michigan  Ann Arbor Michigan 48109-1055"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5221-5498","authenticated-orcid":false,"given":"Nicolai","family":"Lehnert","sequence":"additional","affiliation":[{"name":"Department of Chemistry The University of Michigan  Ann Arbor Michigan 48109-1055"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2024,11,5]]},"reference":[{"key":"e_1_2_3_1_1","doi-asserted-by":"publisher","DOI":"10.1042\/BST0370392"},{"key":"e_1_2_3_2_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr0006627"},{"key":"e_1_2_3_3_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.1c00253"},{"key":"e_1_2_3_4_1","doi-asserted-by":"publisher","DOI":"10.1007\/s00775-015-1329-4"},{"key":"e_1_2_3_5_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.jinorgbio.2014.09.018"},{"key":"e_1_2_3_6_1","doi-asserted-by":"publisher","DOI":"10.1039\/b710047g"},{"key":"e_1_2_3_7_1","doi-asserted-by":"publisher","DOI":"10.1074\/jbc.M110471200"},{"key":"e_1_2_3_8_1","doi-asserted-by":"publisher","DOI":"10.1074\/jbc.M212462200"},{"key":"e_1_2_3_9_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.9b03219"},{"key":"e_1_2_3_10_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0010-8545(00)80259-3"},{"key":"e_1_2_3_11_1","doi-asserted-by":"publisher","DOI":"10.1021\/bi500836z"},{"key":"e_1_2_3_12_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja5022443"},{"key":"e_1_2_3_13_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.8b08567"},{"key":"e_1_2_3_14_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.7b08855"},{"key":"e_1_2_3_15_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.9b13795"},{"key":"e_1_2_3_16_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.7b11464"},{"key":"e_1_2_3_17_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja309782m"},{"key":"e_1_2_3_18_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.1c10388"},{"key":"e_1_2_3_19_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.jinorgbio.2022.111723"},{"key":"e_1_2_3_20_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201812343"},{"key":"e_1_2_3_21_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.inorgchem.7b02333"},{"key":"e_1_2_3_22_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.2c04932"},{"key":"e_1_2_3_23_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.biochem.6b00788"},{"key":"e_1_2_3_24_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja809781r"},{"key":"e_1_2_3_25_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.inorgchem.9b01635"},{"key":"e_1_2_3_26_1","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201911968"},{"key":"e_1_2_3_27_1","doi-asserted-by":"publisher","DOI":"10.1021\/ic500558j"},{"key":"e_1_2_3_28_1","doi-asserted-by":"publisher","DOI":"10.1039\/D1CC03149J"},{"key":"e_1_2_3_29_1","doi-asserted-by":"publisher","DOI":"10.1021\/ic981340c"},{"key":"e_1_2_3_30_1","doi-asserted-by":"publisher","DOI":"10.1021\/ic5002573"}],"container-title":["Angewandte 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