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dc.contributor.author남원우-
dc.contributor.authorShunichi Fukuzumi-
dc.contributor.author김선희-
dc.contributor.author서미숙-
dc.contributor.author김원석-
dc.date.accessioned2020-10-17T16:30:30Z-
dc.date.available2020-10-17T16:30:30Z-
dc.date.issued2020-
dc.identifier.issn1520-5126-
dc.identifier.otherOAK-28013-
dc.identifier.urihttp://dspace.ewha.ac.kr/handle/2015.oak/255474-
dc.description.abstractAcid effects on the chemical properties of metal-oxygen intermediates have attracted much attention recently, such as the enhanced reactivity of high-valent metal(IV)-oxo species by binding proton(s) or Lewis acidic metal ion(s) in redox reactions. Herein, we report for the first time the proton effects of an iron(V)-oxo complex bearing a negatively charged tetraamido macrocyclic ligand (TAML) in oxygen atom transfer (OAT) and electron-transfer (ET) reactions. First, we synthesized and characterized a mononuclear nonheme Fe(V)-oxo TAML complex (1) and its protonated iron(V)-oxo complexes binding two and three protons, which are denoted as 2 and 3, respectively. The protons were found to bind to the TAML ligand of the Fe(V)-oxo species based on spectroscopic characterization, such as resonance Raman, extended X-ray absorption fine structure (EXAFS), and electron paramagnetic resonance (EPR) measurements, along with density functional theory (DFT) calculations. The two-protons binding constant of 1 to produce 2 and the third protonation constant of 2 to produce 3 were determined to be 8.0(7) × 108 M-2 and 10(1) M-1, respectively. The reactivities of the proton-bound iron(V)-oxo complexes were investigated in OAT and ET reactions, showing a dramatic increase in the rate of sulfoxidation of thioanisole derivatives, such as 107 times increase in reactivity when the oxidation of p-CN-thioanisole by 1 was performed in the presence of HOTf (i.e., 200 mM). The one-electron reduction potential of 2 (Ered vs SCE = 0.97 V) was significantly shifted to the positive direction, compared to that of 1 (Ered vs SCE = 0.33 V). Upon further addition of a proton to a solution of 2, a more positive shift of the Ered value was observed with a slope of 47 mV/log([HOTf]). The sulfoxidation of thioanisole derivatives by 2 was shown to proceed via ET from thioanisoles to 2 or direct OAT from 2 to thioanisoles, depending on the ET driving force.-
dc.languageEnglish-
dc.publisherNLM (Medline)-
dc.titleEnhanced Redox Reactivity of a Nonheme Iron(V)-Oxo Complex Binding Proton-
dc.typeArticle-
dc.relation.issue36-
dc.relation.volume142-
dc.relation.indexSCOPUS-
dc.relation.startpage15305-
dc.relation.lastpage15319-
dc.relation.journaltitleJournal of the American Chemical Society-
dc.identifier.doi10.1021/jacs.0c05108-
dc.identifier.scopusid2-s2.0-85090614393-
dc.author.googleXue S.-S.-
dc.author.googleLi X.-X.-
dc.author.googleLee Y.-M.-
dc.author.googleSeo M.S.-
dc.author.googleKim Y.-
dc.author.googleYanagisawa S.-
dc.author.googleKubo M.-
dc.author.googleJeon Y.-K.-
dc.author.googleKim W.-S.-
dc.author.googleSarangi R.-
dc.author.googleKim S.H.-
dc.author.googleFukuzumi S.-
dc.author.googleNam W.-
dc.contributor.scopusid남원우(7006569723)-
dc.contributor.scopusidShunichi Fukuzumi(35430038100)-
dc.contributor.scopusid서미숙(7101805112;8646563100)-
dc.contributor.scopusid김원석(7405812170)-
dc.date.modifydate20201102081004-
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