Full metadata record
DC Field | Value | Language |
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dc.contributor.author | 남원우 | * |
dc.contributor.author | 이용민 | * |
dc.contributor.author | 서미숙 | * |
dc.contributor.author | 김원석 | * |
dc.date.accessioned | 2021-06-07T16:31:42Z | - |
dc.date.available | 2021-06-07T16:31:42Z | - |
dc.date.issued | 2021 | * |
dc.identifier.issn | 0020-1669 | * |
dc.identifier.other | OAK-29322 | * |
dc.identifier.uri | https://dspace.ewha.ac.kr/handle/2015.oak/257668 | - |
dc.description.abstract | Iron(V)-oxo complexes bearing negatively charged tetraamido macrocyclic ligands (TAMLs) have provided excellent opportunities to investigate the chemical properties and the mechanisms of oxidation reactions of mononuclear nonheme iron(V)-oxo intermediates. Herein, we report the differences in chemical properties and reactivities of two iron(V)-oxo TAML complexes differing by modification on the "Head"part of the TAML framework; one has a phenyl group at the "Head"part (1), whereas the other has four methyl groups replacing the phenyl ring (2). The reactivities of 1 and 2 in both C-H bond activation reactions, such as hydrogen atom transfer (HAT) of 1,4-cyclohexadiene, and oxygen atom transfer (OAT) reactions, such as the oxidation of thioanisole and its derivatives, were compared experimentally. Under identical reaction conditions, 1 showed much greater reactivity than 2, such as a 102-fold decrease in HAT and a 105-fold decrease in OAT by replacing the phenyl group (i.e., 1) with four methyl groups (i.e., 2). Then, density functional theory calculations were performed to rationalize the reactivity differences between 1 and 2. Computations reproduced the experimental findings well and revealed that the replacement of the phenyl group in 1 with four methyl groups in 2 not only increased the steric hindrance but also enlarged the energy gap between the electron-donating orbital and the electron-accepting orbital. These two factors, steric hindrance and the orbital energy gap, resulted in differences in the reduction potentials of 1 and 2 and their reactivities in oxidation reactions. © | * |
dc.language | English | * |
dc.publisher | American Chemical Society | * |
dc.title | Ligand Architecture Perturbation Influences the Reactivity of Nonheme Iron(V)-Oxo Tetraamido Macrocyclic Ligand Complexes: A Combined Experimental and Theoretical Study | * |
dc.type | Article | * |
dc.relation.issue | 6 | * |
dc.relation.volume | 60 | * |
dc.relation.index | SCIE | * |
dc.relation.index | SCOPUS | * |
dc.relation.startpage | 4058 | * |
dc.relation.lastpage | 4067 | * |
dc.relation.journaltitle | Inorganic Chemistry | * |
dc.identifier.doi | 10.1021/acs.inorgchem.1c00110 | * |
dc.identifier.wosid | WOS:000630142600058 | * |
dc.identifier.scopusid | 2-s2.0-85102964556 | * |
dc.author.google | Li X.-X. | * |
dc.author.google | Xue S.-S. | * |
dc.author.google | Lu X. | * |
dc.author.google | Seo M.S. | * |
dc.author.google | Lee Y.-M. | * |
dc.author.google | Kim W.-S. | * |
dc.author.google | Cho K.-B. | * |
dc.author.google | Nam W. | * |
dc.contributor.scopusid | 남원우(7006569723) | * |
dc.contributor.scopusid | 이용민(36546331100;35233855500;57192113229) | * |
dc.contributor.scopusid | 서미숙(7101805112) | * |
dc.contributor.scopusid | 김원석(57203484044) | * |
dc.date.modifydate | 20240426135715 | * |