{"@context":{"@vocab":"https://cir.nii.ac.jp/schema/1.0/","rdfs":"http://www.w3.org/2000/01/rdf-schema#","dc":"http://purl.org/dc/elements/1.1/","dcterms":"http://purl.org/dc/terms/","foaf":"http://xmlns.com/foaf/0.1/","prism":"http://prismstandard.org/namespaces/basic/2.0/","cinii":"http://ci.nii.ac.jp/ns/1.0/","datacite":"https://schema.datacite.org/meta/kernel-4/","ndl":"http://ndl.go.jp/dcndl/terms/","jpcoar":"https://github.com/JPCOAR/schema/blob/master/2.0/"},"@id":"https://cir.nii.ac.jp/crid/1363670318922779776.json","@type":"Article","productIdentifier":[{"identifier":{"@type":"DOI","@value":"10.1073/pnas.0709471104"}},{"identifier":{"@type":"URI","@value":"https://pnas.org/doi/pdf/10.1073/pnas.0709471104"}}],"dc:title":[{"@value":"Axial ligand tuning of a nonheme iron(IV)–oxo unit for hydrogen atom abstraction"}],"description":[{"type":"abstract","notation":[{"@value":"<jats:p>\n            The reactivities of mononuclear nonheme iron(IV)–oxo complexes bearing different axial ligands, [Fe\n            <jats:sup>IV</jats:sup>\n            (O)(TMC)(X)]\n            <jats:sup>n+</jats:sup>\n            [where TMC is 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane and X is NCCH\n            <jats:sub>3</jats:sub>\n            (1-NCCH\n            <jats:sub>3</jats:sub>\n            ), CF\n            <jats:sub>3</jats:sub>\n            COO\n            <jats:sup>−</jats:sup>\n            (1-OOCCF\n            <jats:sub>3</jats:sub>\n            ), or N\n            <jats:sub arrange=\"stack\">3</jats:sub>\n            <jats:sup arrange=\"stack\">−</jats:sup>\n            (1-N\n            <jats:sub>3</jats:sub>\n            )], and [Fe\n            <jats:sup>IV</jats:sup>\n            (O)(TMCS)]\n            <jats:sup>+</jats:sup>\n            (1′-SR) (where TMCS is 1-mercaptoethyl-4,8,11-trimethyl-1,4,8,11-tetraazacyclotetradecane), have been investigated with respect to oxo-transfer to PPh\n            <jats:sub>3</jats:sub>\n            and hydrogen atom abstraction from phenol O\n            <jats:inline-graphic xmlns:xlink=\"http://www.w3.org/1999/xlink\" xlink:href=\"cjs0807.gif\"/>\n            H and alkylaromatic C\n            <jats:inline-graphic xmlns:xlink=\"http://www.w3.org/1999/xlink\" xlink:href=\"cjs0807.gif\"/>\n            H bonds. These reactivities were significantly affected by the identity of the axial ligands, but the reactivity trends differed markedly. In the oxidation of PPh\n            <jats:sub>3</jats:sub>\n            , the reactivity order of 1-NCCH\n            <jats:sub>3</jats:sub>\n            > 1-OOCCF\n            <jats:sub>3</jats:sub>\n            > 1-N\n            <jats:sub>3</jats:sub>\n            > 1′-SR was observed, reflecting a decrease in the electrophilicity of iron(IV)–oxo unit upon replacement of CH\n            <jats:sub>3</jats:sub>\n            CN with an anionic axial ligand. Surprisingly, the reactivity order was inverted in the oxidation of alkylaromatic C\n            <jats:inline-graphic xmlns:xlink=\"http://www.w3.org/1999/xlink\" xlink:href=\"cjs0807.gif\"/>\n            H and phenol O\n            <jats:inline-graphic xmlns:xlink=\"http://www.w3.org/1999/xlink\" xlink:href=\"cjs0807.gif\"/>\n            H bonds, i.e., 1′-SR > 1-N\n            <jats:sub>3</jats:sub>\n            > 1-OOCCF\n            <jats:sub>3</jats:sub>\n            > 1-NCCH\n            <jats:sub>3</jats:sub>\n            . Furthermore, a good correlation was observed between the reactivities of iron(IV)–oxo species in H atom abstraction reactions and their reduction potentials,\n            <jats:italic>E</jats:italic>\n            <jats:sub>p,c</jats:sub>\n            , with the most reactive 1′-SR complex exhibiting the lowest potential. In other words, the more electron-donating the axial ligand is, the more reactive the iron(IV)–oxo species becomes in H atom abstraction. Quantum mechanical calculations show that a two-state reactivity model applies to this series of complexes, in which a triplet ground state and a nearby quintet excited-state both contribute to the reactivity of the complexes. The inverted reactivity order in H atom abstraction can be rationalized by a decreased triplet-quintet gap with the more electron-donating axial ligand, which increases the contribution of the much more reactive quintet state and enhances the overall reactivity.\n          </jats:p>"}]}],"creator":[{"@id":"https://cir.nii.ac.jp/crid/1380013199357506312","@type":"Researcher","foaf:name":[{"@value":"Chivukula V. Sastri"}],"jpcoar:affiliationName":[{"@value":"Department of Chemistry, Division of Nano Sciences, and Center for Biomimetic Systems, Ewha Womans University, Seoul 120-750, Korea;"}]},{"@id":"https://cir.nii.ac.jp/crid/1380013199357506306","@type":"Researcher","foaf:name":[{"@value":"Jimin Lee"}],"jpcoar:affiliationName":[{"@value":"Department of Chemistry, Division of Nano Sciences, and Center for Biomimetic Systems, Ewha Womans University, Seoul 120-750, Korea;"}]},{"@id":"https://cir.nii.ac.jp/crid/1380013199357506309","@type":"Researcher","foaf:name":[{"@value":"Kyungeun Oh"}],"jpcoar:affiliationName":[{"@value":"Department of Chemistry, Division of Nano Sciences, and Center for Biomimetic Systems, Ewha Womans University, Seoul 120-750, Korea;"}]},{"@id":"https://cir.nii.ac.jp/crid/1380013199357506317","@type":"Researcher","foaf:name":[{"@value":"Yoon Jin Lee"}],"jpcoar:affiliationName":[{"@value":"Department of Chemistry, Division of Nano Sciences, and Center for Biomimetic Systems, Ewha Womans University, Seoul 120-750, Korea;"}]},{"@id":"https://cir.nii.ac.jp/crid/1380013199357506314","@type":"Researcher","foaf:name":[{"@value":"Junghyun Lee"}],"jpcoar:affiliationName":[{"@value":"Department of Chemistry and Interdisciplinary Program of Integrated Biotechnology, Sogang University, Seoul 121-742, Korea;"}]},{"@id":"https://cir.nii.ac.jp/crid/1380013199357506304","@type":"Researcher","foaf:name":[{"@value":"Timothy A. Jackson"}],"jpcoar:affiliationName":[{"@value":"Department of Chemistry and Center for Metals in Biocatalysis, University of Minnesota, Minneapolis, MN 55455;"}]},{"@id":"https://cir.nii.ac.jp/crid/1380013199357506316","@type":"Researcher","foaf:name":[{"@value":"Kallol Ray"}],"jpcoar:affiliationName":[{"@value":"Department of Chemistry and Center for Metals in Biocatalysis, University of Minnesota, Minneapolis, MN 55455;"}]},{"@id":"https://cir.nii.ac.jp/crid/1380013199357506305","@type":"Researcher","foaf:name":[{"@value":"Hajime Hirao"}],"jpcoar:affiliationName":[{"@value":"Department of Chemistry and Lise Meitner-Minerva Center for Computational Quantum Chemistry, Hebrew University of Jerusalem, Jerusalem 91904, Israel; and"}]},{"@id":"https://cir.nii.ac.jp/crid/1380013199357506311","@type":"Researcher","foaf:name":[{"@value":"Woonsup Shin"}],"jpcoar:affiliationName":[{"@value":"Department of Chemistry and Interdisciplinary Program of Integrated Biotechnology, Sogang University, Seoul 121-742, Korea;"}]},{"@id":"https://cir.nii.ac.jp/crid/1380013199357506308","@type":"Researcher","foaf:name":[{"@value":"Jason A. Halfen"}],"jpcoar:affiliationName":[{"@value":"Department of Chemistry, University of Wisconsin, Eau Claire, WI 54702"}]},{"@id":"https://cir.nii.ac.jp/crid/1380013199357506307","@type":"Researcher","foaf:name":[{"@value":"Jinheung Kim"}],"jpcoar:affiliationName":[{"@value":"Department of Chemistry, Division of Nano Sciences, and Center for Biomimetic Systems, Ewha Womans University, Seoul 120-750, Korea;"}]},{"@id":"https://cir.nii.ac.jp/crid/1380013199357506310","@type":"Researcher","foaf:name":[{"@value":"Lawrence Que"}],"jpcoar:affiliationName":[{"@value":"Department of Chemistry and Center for Metals in Biocatalysis, University of Minnesota, Minneapolis, MN 55455;"}]},{"@id":"https://cir.nii.ac.jp/crid/1380013199357506313","@type":"Researcher","foaf:name":[{"@value":"Sason Shaik"}],"jpcoar:affiliationName":[{"@value":"Department of Chemistry and Lise Meitner-Minerva Center for Computational Quantum Chemistry, Hebrew University of Jerusalem, Jerusalem 91904, Israel; and"}]},{"@id":"https://cir.nii.ac.jp/crid/1380013199357506315","@type":"Researcher","foaf:name":[{"@value":"Wonwoo Nam"}],"jpcoar:affiliationName":[{"@value":"Department of Chemistry, Division of Nano Sciences, and Center for Biomimetic Systems, Ewha Womans University, Seoul 120-750, Korea;"}]}],"publication":{"publicationIdentifier":[{"@type":"PISSN","@value":"00278424"},{"@type":"EISSN","@value":"10916490"}],"prism:publicationName":[{"@value":"Proceedings of the National Academy of Sciences"}],"dc:publisher":[{"@value":"Proceedings of the National Academy of Sciences"}],"prism:publicationDate":"2007-12-04","prism:volume":"104","prism:number":"49","prism:startingPage":"19181","prism:endingPage":"19186"},"reviewed":"false","url":[{"@id":"https://pnas.org/doi/pdf/10.1073/pnas.0709471104"}],"createdAt":"2007-11-29","modifiedAt":"2022-04-12","relatedProduct":[{"@id":"https://cir.nii.ac.jp/crid/1050864247416110464","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@language":"en","@value":"Geometric, electronic and spin structures of the CaMn4O5 catalyst for water oxidation in oxygen-evolving photosystem II. Interplay between experiments and theoretical computations"}]},{"@id":"https://cir.nii.ac.jp/crid/1360002215850329216","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@value":"Amphoteric reactivity of metal–oxygen complexes in oxidation reactions"}]},{"@id":"https://cir.nii.ac.jp/crid/1360002216643432576","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@value":"Theoretical Study of Mononuclear Nickel(I), Nickel(0), Copper(I), and Cobalt(I) Dioxygen Complexes: New Insight into Differences and Similarities in Geometry and Bonding Nature"}]},{"@id":"https://cir.nii.ac.jp/crid/1360004233576800256","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@value":"Reactivity comparison of high-valent iron(iv)-oxo complexes bearing N-tetramethylated cyclam ligands with different ring size"}]},{"@id":"https://cir.nii.ac.jp/crid/1360009142705720960","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@value":"Selective catalytic 2e<sup>−</sup>-oxidation of organic substrates by an Fe<sup>II</sup> complex having an N-heterocyclic carbene ligand in water"}]},{"@id":"https://cir.nii.ac.jp/crid/1360283691583403008","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@value":"Efficient Epoxidation of Styrene Derivatives by a Nonheme Iron(IV)-Oxo Complex via Proton-Coupled Electron Transfer with Triflic Acid"}]},{"@id":"https://cir.nii.ac.jp/crid/1360283691866325888","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@value":"An amphoteric reactivity of a mixed-valent bis(μ-oxo)dimanganese(<scp>iii</scp>,<scp>iv</scp>) complex acting as an electrophile and a nucleophile"}]},{"@id":"https://cir.nii.ac.jp/crid/1360285708190161408","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@value":"Brønsted Acid-Promoted C–H Bond Cleavage via Electron Transfer from Toluene Derivatives to a Protonated Nonheme Iron(IV)-Oxo Complex with No Kinetic Isotope Effect"}]},{"@id":"https://cir.nii.ac.jp/crid/1360565166596885120","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@value":"Unified View of Oxidative C–H Bond Cleavage and Sulfoxidation by a Nonheme Iron(IV)–Oxo Complex via Lewis Acid-Promoted Electron Transfer"}]},{"@id":"https://cir.nii.ac.jp/crid/1360565166597440512","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@value":"Factors Affecting Hydrogen-Tunneling Contribution in Hydroxylation Reactions Promoted by Oxoiron(IV) Porphyrin π-Cation Radical Complexes"}]},{"@id":"https://cir.nii.ac.jp/crid/1360565166611881216","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@value":"[Fe<sup>IV</sup>═O(TBC)(CH<sub>3</sub>CN)]<sup>2+</sup>: Comparative Reactivity of Iron(IV)-Oxo Species with Constrained Equatorial Cyclam Ligation"}]},{"@id":"https://cir.nii.ac.jp/crid/1360567183080020736","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@value":"Importance of the Reactant-State Potentials of Chromium(V)–Oxo Complexes to Determine the Reactivity in Hydrogen-Atom Transfer Reactions"}]},{"@id":"https://cir.nii.ac.jp/crid/1360567183169518336","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@value":"Mechanistic Insights into C–H Oxidations by Ruthenium(III)-Pterin Complexes: Impact of Basicity of the Pterin Ligand and Electron Acceptability of the Metal Center on the Transition States"}]},{"@id":"https://cir.nii.ac.jp/crid/1360567183536257280","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@value":"Synthesis, stability and reactivity of the first mononuclear nonheme oxoiron(iv) species with monoamido ligation: a putative reactive species generated from iron-bleomycin"}]},{"@id":"https://cir.nii.ac.jp/crid/1360848658122204032","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@value":"Fe<sup>III</sup> Bipyrrolidine Phenoxide Complexes and Their Oxidized Analogues"}]},{"@id":"https://cir.nii.ac.jp/crid/1360848658147602432","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@value":"Redox Reactivity of a Mononuclear Manganese-Oxo Complex Binding Calcium Ion and Other Redox-Inactive Metal Ions"}]},{"@id":"https://cir.nii.ac.jp/crid/1360848658493777024","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@value":"Chromium(v)-oxo and chromium(iii)-superoxo complexes bearing a macrocyclic TMC ligand in hydrogen atom abstraction reactions"}]},{"@id":"https://cir.nii.ac.jp/crid/1360861707154612224","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@value":"Stacking of a Cofacially Stacked Iron Phthalocyanine Dimer on Graphite Achieved High Catalytic CH\n                    <sub>4</sub>\n                    Oxidation Activity Comparable to That of pMMO"}]},{"@id":"https://cir.nii.ac.jp/crid/1360865815510134272","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@value":"Effect of porphyrin ligands on the catalytic CH<sub>4</sub> oxidation activity of monocationic μ-nitrido-bridged iron porphyrinoid dimers by using H<sub>2</sub>O<sub>2</sub> as an oxidant"}]}],"dataSourceIdentifier":[{"@type":"CROSSREF","@value":"10.1073/pnas.0709471104"},{"@type":"CROSSREF","@value":"10.1039/c3dt50750e_references_DOI_YyHCVC7jxh2Th7OdCazEoMKeTaf"},{"@type":"CROSSREF","@value":"10.1021/jacs.6b03785_references_DOI_YyHCVC7jxh2Th7OdCazEoMKeTaf"},{"@type":"CROSSREF","@value":"10.1021/ic500663x_references_DOI_YyHCVC7jxh2Th7OdCazEoMKeTaf"},{"@type":"CROSSREF","@value":"10.1039/d0cc03289a_references_DOI_YyHCVC7jxh2Th7OdCazEoMKeTaf"},{"@type":"CROSSREF","@value":"10.1039/c5dt04292e_references_DOI_YyHCVC7jxh2Th7OdCazEoMKeTaf"},{"@type":"CROSSREF","@value":"10.1021/acs.inorgchem.5b00504_references_DOI_YyHCVC7jxh2Th7OdCazEoMKeTaf"},{"@type":"CROSSREF","@value":"10.1016/j.ccr.2022.214742_references_DOI_YyHCVC7jxh2Th7OdCazEoMKeTaf"},{"@type":"CROSSREF","@value":"10.1039/c4cc01409j_references_DOI_YyHCVC7jxh2Th7OdCazEoMKeTaf"},{"@type":"CROSSREF","@value":"10.1021/ic402059b_references_DOI_YyHCVC7jxh2Th7OdCazEoMKeTaf"},{"@type":"CROSSREF","@value":"10.1039/c1sc00386k_references_DOI_YyHCVC7jxh2Th7OdCazEoMKeTaf"},{"@type":"CROSSREF","@value":"10.1021/jacsau.2c00618_references_DOI_YyHCVC7jxh2Th7OdCazEoMKeTaf"},{"@type":"CROSSREF","@value":"10.1039/d3dt04313d_references_DOI_YyHCVC7jxh2Th7OdCazEoMKeTaf"},{"@type":"CROSSREF","@value":"10.1021/ja311662w_references_DOI_YyHCVC7jxh2Th7OdCazEoMKeTaf"},{"@type":"CROSSREF","@value":"10.1016/j.ccr.2018.03.003_references_DOI_YyHCVC7jxh2Th7OdCazEoMKeTaf"},{"@type":"CROSSREF","@value":"10.1021/jacs.8b11492_references_DOI_YyHCVC7jxh2Th7OdCazEoMKeTaf"},{"@type":"CROSSREF","@value":"10.1021/ic403124u_references_DOI_YyHCVC7jxh2Th7OdCazEoMKeTaf"},{"@type":"CROSSREF","@value":"10.1021/acs.inorgchem.8b02453_references_DOI_YyHCVC7jxh2Th7OdCazEoMKeTaf"},{"@type":"CROSSREF","@value":"10.1021/ic501737j_references_DOI_YyHCVC7jxh2Th7OdCazEoMKeTaf"},{"@type":"CROSSREF","@value":"10.1021/ja3046298_references_DOI_YyHCVC7jxh2Th7OdCazEoMKeTaf"}]}