{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,3,18]],"date-time":"2026-03-18T12:51:43Z","timestamp":1773838303773,"version":"3.50.1"},"reference-count":49,"publisher":"Wiley","issue":"52","license":[{"start":{"date-parts":[[2022,7,27]],"date-time":"2022-07-27T00:00:00Z","timestamp":1658880000000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"funder":[{"DOI":"10.13039\/501100004663","name":"Ministry of Science and Technology, Taiwan","doi-asserted-by":"publisher","award":["109-2113-M-005-006-"],"award-info":[{"award-number":["109-2113-M-005-006-"]}],"id":[{"id":"10.13039\/501100004663","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["chemistry-europe.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Chemistry A European J"],"published-print":{"date-parts":[[2022,9,16]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>Saddle\u2010shaped hemes have been discovered in the structures of most peroxidases. How such a macrocycle deformation affects the reaction of Fe<jats:sup>III<\/jats:sup> hemes with hydrogen peroxide (H<jats:sub>2<\/jats:sub>O<jats:sub>2<\/jats:sub>) to form high\u2010valent Fe\u2010oxo species remains uncertain. Through examination of the ESI\u2010MS spectra, absorption changes and <jats:sup>1<\/jats:sup>H NMR chemical shifts, we investigated the reactions of two Fe<jats:sup>III<\/jats:sup> porphyrins with different degrees of saddling deformation, namely Fe<jats:sup>III<\/jats:sup>(OETPP)ClO<jats:sub>4<\/jats:sub> (<jats:bold>1<jats:sup>OE<\/jats:sup><\/jats:bold>) and Fe<jats:sup>III<\/jats:sup>(OMTPP)ClO<jats:sub>4<\/jats:sub> (<jats:bold>1<jats:sup>OM<\/jats:sup><\/jats:bold>), with <jats:italic>tert<\/jats:italic>\u2010butyl hydroperoxide (<jats:italic>t<\/jats:italic>BuOOH) in CH<jats:sub>2<\/jats:sub>Cl<jats:sub>2<\/jats:sub> at \u221240\u2009\u00b0C, which quickly resulted in O\u2212O bond homolysis from a highly unstable Fe<jats:sup>III<\/jats:sup>\u2010alkylperoxo intermediate, Fe<jats:sup>III<\/jats:sup>\u2010O(H)OR (<jats:bold>2<\/jats:bold>) into Fe<jats:sup>IV<\/jats:sup>\u2010oxo porphyrins (<jats:bold>3<\/jats:bold>). Insight into the reaction mechanism was obtained from [<jats:italic>t<\/jats:italic>BuOOH]\u2010dependent kinetics. At \u221240\u2009\u00b0C, the reaction of <jats:bold>1<jats:sup>OE<\/jats:sup><\/jats:bold> with <jats:italic>t<\/jats:italic>BuOOH exhibited an equilibrium constant (<jats:italic>K<jats:sub>a<\/jats:sub><\/jats:italic>=362.3\u2005M<jats:sup>\u22121<\/jats:sup>) and rate constant (<jats:italic>k<\/jats:italic>=1.87\u00d710<jats:sup>\u22122<\/jats:sup>\u2005s<jats:sup>M\u2212&gt;1<\/jats:sup>) for the homolytic cleavage of the <jats:bold>2<\/jats:bold> O\u2212O bond that were 2.1 and 1.4 times higher, respectively, than those exhibited by <jats:bold>1<jats:sup>OM<\/jats:sup><\/jats:bold> (<jats:italic>K<\/jats:italic><jats:sub>a<\/jats:sub>=171.8\u2005M<jats:sup>\u22121<\/jats:sup> and <jats:italic>k<\/jats:italic>=1.36\u00d710<jats:sup>\u22122<\/jats:sup>\u2009\u2009s<jats:sup>\u22121<\/jats:sup>). DFT calculations indicated that an Fe<jats:sup>III<\/jats:sup> porphyrin with greater saddling deformation can achieve a higher HOMO ([Fe(d<jats:inline-graphic xmlns:xlink=\"http:\/\/www.w3.org\/1999\/xlink\" xlink:href=\"graphic\/chem202201139-math-0001.png\" xlink:title=\"urn:x-wiley:09476539:media:chem202201139:chem202201139-math-0001\"\/>\n,d<jats:inline-graphic xmlns:xlink=\"http:\/\/www.w3.org\/1999\/xlink\" xlink:href=\"graphic\/chem202201139-math-0002.png\" xlink:title=\"urn:x-wiley:09476539:media:chem202201139:chem202201139-math-0002\"\/>\n)\u2010porphyrin(a<jats:sub>2u<\/jats:sub>)]) to strengthen the orbital interaction with the LUMO (O\u2212O bond \u03c3*) to facilitate O\u2212O cleavage.<\/jats:p>","DOI":"10.1002\/chem.202201139","type":"journal-article","created":{"date-parts":[[2022,6,27]],"date-time":"2022-06-27T08:17:19Z","timestamp":1656317839000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":3,"title":["Modeling Heme Peroxidase: Heme Saddling Facilitates Reactions with Hyperperoxides To Form High\u2010Valent Fe<sup>IV<\/sup>\u2010Oxo Species"],"prefix":"10.1002","volume":"28","author":[{"given":"Chang\u2010Quan","family":"Wu","sequence":"first","affiliation":[{"name":"Department of Chemistry National Chung Hsing University  145 Xingda Rd., South Dist. Taichung City 402 Taiwan (R.O.C."}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Yi\u2010Wen","family":"Wu","sequence":"additional","affiliation":[{"name":"Department of Chemistry National Chung Hsing University  145 Xingda Rd., South Dist. Taichung City 402 Taiwan (R.O.C."}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Xuan\u2010Han","family":"He","sequence":"additional","affiliation":[{"name":"Department of Chemistry National Chung Hsing University  145 Xingda Rd., South Dist. Taichung City 402 Taiwan (R.O.C."}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Ruo\u2010Ting","family":"Hong","sequence":"additional","affiliation":[{"name":"Department of Chemistry National Chung Hsing University  145 Xingda Rd., South Dist. Taichung City 402 Taiwan (R.O.C."}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Hao\u2010Chien","family":"Lee","sequence":"additional","affiliation":[{"name":"Department of Chemistry National Chung Hsing University  145 Xingda Rd., South Dist. Taichung City 402 Taiwan (R.O.C."}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Kang\u2010Yen","family":"Feng","sequence":"additional","affiliation":[{"name":"Department of Chemistry National Chung Hsing University  145 Xingda Rd., South Dist. Taichung City 402 Taiwan (R.O.C."}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-3472-4221","authenticated-orcid":false,"given":"Peter","family":"Ping\u2010Yu Chen","sequence":"additional","affiliation":[{"name":"Department of Chemistry National Chung Hsing University  145 Xingda Rd., South Dist. 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