{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,14]],"date-time":"2025-10-14T00:57:01Z","timestamp":1760403421760,"version":"build-2065373602"},"reference-count":53,"publisher":"Wiley","issue":"46","license":[{"start":{"date-parts":[[2018,11,9]],"date-time":"2018-11-09T00:00:00Z","timestamp":1541721600000},"content-version":"am","delay-in-days":330,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#am"},{"start":{"date-parts":[[2017,12,14]],"date-time":"2017-12-14T00:00:00Z","timestamp":1513209600000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"funder":[{"DOI":"10.13039\/100000001","name":"National Science Foundation","doi-asserted-by":"publisher","award":["CHE\u20100821487"],"award-info":[{"award-number":["CHE\u20100821487"]}],"id":[{"id":"10.13039\/100000001","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/100000002","name":"National Institutes of Health","doi-asserted-by":"publisher","award":["R15GM112395"],"award-info":[{"award-number":["R15GM112395"]}],"id":[{"id":"10.13039\/100000002","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["chemistry-europe.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Eur J Inorg Chem"],"published-print":{"date-parts":[[2017,12,15]]},"abstract":"<jats:p>We previously reported the spin\u2010crossover (SC) properties of [Fe<jats:sup>II<\/jats:sup>(tacn)<jats:sub>2<\/jats:sub>](OTf)<jats:sub>2<\/jats:sub> (<jats:bold>1<\/jats:bold>) (tacn = 1,4,7\u2010triazacyclononane). Upon heating under dynamic vacuum, <jats:bold>1<\/jats:bold> undergoes oxidation to generate a low\u2010spin iron(III) complex. The oxidation of the iron center was found to be facilitated by initial oxidation of the ligand through loss of a H atom. The resulting complex was hypothesized to have the formulation [Fe<jats:sup>III<\/jats:sup>(tacn)(tacn\u2010H)](OTf)<jats:sub>2<\/jats:sub> (<jats:bold>2<\/jats:bold>) where tacn\u2010H is <jats:italic>N<\/jats:italic>\u2010deprotonated tacn. The formulation was confirmed by ESI\u2010MS. The powder EPR spectrum of the oxidized product at 77 K reveals the formation of a low\u2010spin iron(III) species with rhombic spectrum (<jats:italic>g<\/jats:italic> = 1.98, 2.10, 2.19). We have indirectly detected H<jats:sub>2<\/jats:sub> formation during the heating of <jats:bold>1<\/jats:bold> by reacting the headspace with HgO. Formation of water (<jats:sup>1<\/jats:sup>H NMR in anhydrous [D<jats:sub>6<\/jats:sub>]DMSO) and elemental mercury were observed. To further support this claim, we independently synthesized [Fe<jats:sup>III<\/jats:sup>(tacn)<jats:sub>2<\/jats:sub>](OTf)<jats:sub>3<\/jats:sub> (<jats:bold>3<\/jats:bold>) and treated it with one equivalent of base yielding <jats:bold>2<\/jats:bold>. The structures of <jats:bold>3<\/jats:bold> were characterized by X\u2010ray crystallography. Compound <jats:bold>2<\/jats:bold> also exhibits a low\u2010spin iron(III) rhombic signal (<jats:italic>g<\/jats:italic> = 1.97, 2.11, 2.23) in DMF at 77 K. Variable temperature magnetic susceptibility measurements indicate that <jats:bold>3<\/jats:bold> undergoes gradual spin increase from 2 to 400 K. DFT studies indicate that the deprotonated nitrogen in <jats:bold>2<\/jats:bold> forms a bond to iron(III) exhibiting double\u2010bond character (Fe\u2013N, 1.807 \u00c5).<\/jats:p>","DOI":"10.1002\/ejic.201701190","type":"journal-article","created":{"date-parts":[[2017,11,9]],"date-time":"2017-11-09T14:26:36Z","timestamp":1510237596000},"page":"5529-5535","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":2,"title":["Thermally Induced Oxidation of [Fe<sup>II<\/sup>(tacn)<sub>2<\/sub>](OTf)<sub>2<\/sub> (tacn = 1,4,7\u2010triazacyclononane)"],"prefix":"10.1002","volume":"2017","author":[{"given":"Jia","family":"Li","sequence":"first","affiliation":[{"name":"Department of Chemistry Oakland University  48309\u20104477 Rochester MI USA"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Atanu","family":"Banerjee","sequence":"additional","affiliation":[{"name":"Department of Chemistry Oakland University  48309\u20104477 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