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Many hs\u2010{FeNO}<jats:sup>8<\/jats:sup> complexes disproportionate by forming dinitrosyl iron complexes (DNICs), but the mechanism of this reaction is not understood. While investigating this process, we isolated a new type of non\u2010heme iron nitrosyl complex that is stabilized by an unexpected spin\u2010state change. Upon reduction of the hs\u2010{FeNO}<jats:sup>7<\/jats:sup> complex, [Fe(TPA)(NO)(OTf)](OTf) (<jats:bold>1<\/jats:bold>), the N\u2010O stretching band vanishes, but no sign of DNIC or N<jats:sub>2<\/jats:sub>O formation is observed. Instead, the dimer, [Fe<jats:sub>2<\/jats:sub>(TPA)<jats:sub>2<\/jats:sub>(NO)<jats:sub>2<\/jats:sub>](OTf)<jats:sub>2<\/jats:sub> (<jats:bold>2<\/jats:bold>) could be isolated and structurally characterized. We propose that <jats:bold>2<\/jats:bold> is formed from dimerization of the hs\u2010{FeNO}<jats:sup>8<\/jats:sup> intermediate, followed by a spin state change of the iron centers to low\u2010spin (ls), and speculate that <jats:bold>2<\/jats:bold> models intermediates in hs\u2010{FeNO}<jats:sup>8<\/jats:sup> complexes that precede the disproportionation reaction.<\/jats:p>","DOI":"10.1002\/anie.201911968","type":"journal-article","created":{"date-parts":[[2019,9,24]],"date-time":"2019-09-24T17:30:35Z","timestamp":1569346235000},"page":"17695-17699","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":20,"title":["The Fe<sub>2<\/sub>(NO)<sub>2<\/sub> Diamond Core: A Unique Structural Motif In Non\u2010Heme Iron\u2013NO Chemistry"],"prefix":"10.1002","volume":"58","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-8914-3045","authenticated-orcid":false,"given":"Hai T.","family":"Dong","sequence":"first","affiliation":[{"name":"Department of Chemistry and Department of Biophysics The University of Michigan  Ann Arbor Michigan 48109-1055 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Amy L.","family":"Speelman","sequence":"additional","affiliation":[{"name":"Department of Chemistry and Department of Biophysics The University of Michigan  Ann Arbor Michigan 48109-1055 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Claire E.","family":"Kozemchak","sequence":"additional","affiliation":[{"name":"Department of Chemistry and Department of Biophysics The University of Michigan  Ann Arbor Michigan 48109-1055 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Debangsu","family":"Sil","sequence":"additional","affiliation":[{"name":"Department of Chemistry and Department of Biochemistry and Molecular Biology The Pennsylvania State University  University Park Pennsylvania 16802 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Carsten","family":"Krebs","sequence":"additional","affiliation":[{"name":"Department of Chemistry and Department of Biochemistry and Molecular Biology The Pennsylvania State University  University Park Pennsylvania 16802 USA"}],"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 and Department of Biophysics The University of Michigan  Ann Arbor Michigan 48109-1055 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2019,10,23]]},"reference":[{"key":"e_1_2_2_1_1","unstructured":"\u00a0"},{"key":"e_1_2_2_2_2","volume-title":"Nitric Oxide: Biology and Pathobiology","author":"Ignarro 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