Full metadata record
DC Field | Value | Language |
---|---|---|
dc.contributor.author | 남원우 | * |
dc.contributor.author | Shunichi Fukuzumi | * |
dc.contributor.author | 김선희 | * |
dc.contributor.author | 서미숙 | * |
dc.contributor.author | 김원석 | * |
dc.date.accessioned | 2020-10-17T16:30:30Z | - |
dc.date.available | 2020-10-17T16:30:30Z | - |
dc.date.issued | 2020 | * |
dc.identifier.issn | 0002-7863 | * |
dc.identifier.issn | 1520-5126 | * |
dc.identifier.other | OAK-28013 | * |
dc.identifier.uri | https://dspace.ewha.ac.kr/handle/2015.oak/255474 | - |
dc.description.abstract | Acid 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) x 10(8) 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 (E-red vs SCE = 0.97 V) was significantly shifted to the positive direction, compared to that of 1 (E-red vs SCE = 0.33 V). Upon further addition of a proton to a solution of 2, a more positive shift of the E-red 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.language | English | * |
dc.publisher | AMER CHEMICAL SOC | * |
dc.title | Enhanced Redox Reactivity of a Nonheme Iron(V)-Oxo Complex Binding Proton | * |
dc.type | Article | * |
dc.relation.issue | 36 | * |
dc.relation.volume | 142 | * |
dc.relation.index | SCIE | * |
dc.relation.index | SCOPUS | * |
dc.relation.startpage | 15305 | * |
dc.relation.lastpage | 15319 | * |
dc.relation.journaltitle | JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | * |
dc.identifier.doi | 10.1021/jacs.0c05108 | * |
dc.identifier.wosid | WOS:000571437600014 | * |
dc.identifier.scopusid | 2-s2.0-85090614393 | * |
dc.author.google | Xue, Shan-Shan | * |
dc.author.google | Li, Xiao-Xi | * |
dc.author.google | Lee, Yong-Min | * |
dc.author.google | Seo, Mi Sook | * |
dc.author.google | Kim, Yujeong | * |
dc.author.google | Yanagisawa, Sachiko | * |
dc.author.google | Kubo, Minoru | * |
dc.author.google | Jeon, Young-Kyo | * |
dc.author.google | Kim, Won-Suk | * |
dc.author.google | Sarangi, Ritimukta | * |
dc.author.google | Kim, Sun Hee | * |
dc.author.google | Fukuzumi, Shunichi | * |
dc.author.google | Nam, Wonwoo | * |
dc.contributor.scopusid | 남원우(7006569723) | * |
dc.contributor.scopusid | Shunichi Fukuzumi(35430038100;58409757400) | * |
dc.contributor.scopusid | 김선희(57205324645;57196230818) | * |
dc.contributor.scopusid | 서미숙(7101805112) | * |
dc.contributor.scopusid | 김원석(57203484044) | * |
dc.date.modifydate | 20240405124941 | * |