{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,24]],"date-time":"2026-09-24T04:26:34Z","timestamp":1790223994719,"version":"4.1.0"},"reference-count":27,"publisher":"MDPI AG","issue":"12","license":[{"start":{"date-parts":[[2023,6,14]],"date-time":"2023-06-14T00:00:00Z","timestamp":1686700800000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/100000002","name":"National Institutes of Health USA","doi-asserted-by":"publisher","award":["GM050781"],"award-info":[{"award-number":["GM050781"]}],"id":[{"id":"10.13039\/100000002","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Molecules"],"abstract":"<jats:p>Non-heme Fe monooxygenases activate C\u2013H bonds using intermediates with high-spin FeIV\u2013oxido centers. To mimic these sites, a new tripodal ligand [pop]3\u2212 was prepared that contains three phosphoryl amido groups that are capable of stabilizing metal centers in high oxidation states. The ligand was used to generate [FeIVpop(O)]\u2212, a new FeIV\u2013oxido complex with an S = 2 spin ground state. Spectroscopic measurements, which included low-temperature absorption and electron paramagnetic resonance spectroscopy, supported the assignment of a high-spin FeIV center. The complex showed reactivity with benzyl alcohol as the external substrate but not with related compounds (e.g., ethyl benzene and benzyl methyl ether), suggesting the possibility that hydrogen bonding interaction(s) between the substrate and [FeIVpop(O)]\u2212 was necessary for reactivity. These results exemplify the potential role of the secondary coordination sphere in metal-mediated processes.<\/jats:p>","DOI":"10.3390\/molecules28124755","type":"journal-article","created":{"date-parts":[[2023,6,14]],"date-time":"2023-06-14T02:26:56Z","timestamp":1686709616000},"page":"4755","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":6,"title":["Selective C\u2013H Bond Cleavage with a High-Spin FeIV\u2013Oxido Complex"],"prefix":"10.3390","volume":"28","author":[{"given":"Chen","family":"Sun","sequence":"first","affiliation":[{"name":"Department of Chemistry, University of California-Irvine, Irvine, CA 92697, USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jennifer L.","family":"Jaimes","sequence":"additional","affiliation":[{"name":"Department of Chemistry, University of California-Irvine, Irvine, CA 92697, USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Alec H.","family":"Follmer","sequence":"additional","affiliation":[{"name":"Department of Chemistry, University of California-Irvine, Irvine, CA 92697, USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Joseph W.","family":"Ziller","sequence":"additional","affiliation":[{"name":"Department of Chemistry, University of California-Irvine, Irvine, CA 92697, USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5049-9952","authenticated-orcid":false,"given":"Andrew S.","family":"Borovik","sequence":"additional","affiliation":[{"name":"Department of Chemistry, University of California-Irvine, Irvine, CA 92697, USA"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"1968","published-online":{"date-parts":[[2023,6,14]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"14326","DOI":"10.1073\/pnas.1212693109","article-title":"\u03c0-Frontier Molecular Orbitals in S = 2 Ferryl Species and Elucidation of Their Contributions to Reactivity","volume":"109","author":"Srnec","year":"2012","journal-title":"Proc. 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