Full metadata record
DC Field | Value | Language |
---|---|---|
dc.contributor.author | 남원우 | * |
dc.contributor.author | Shunichi Fukuzumi | * |
dc.contributor.author | 이용민 | * |
dc.date.accessioned | 2016-08-29T12:08:38Z | - |
dc.date.available | 2016-08-29T12:08:38Z | - |
dc.date.issued | 2016 | * |
dc.identifier.issn | 0002-7863 | * |
dc.identifier.other | OAK-19067 | * |
dc.identifier.uri | https://dspace.ewha.ac.kr/handle/2015.oak/231756 | - |
dc.description.abstract | A mononuclear non-heme manganese(V)-oxo complex, [Mn-V(O)(TAML)](-) (1), was synthesized by activating dioxygen in the presence of olefins with weak allylic C-H bonds and characterized structurally and spectroscopically. In mechanistic studies, the formation rate of 1 was found to depend on the allylic C-H bond dissociation energies (BDEs) of olefins, and a kinetic isotope effect (KIE) value of 16 was obtained in the reactions of cyclohexene and cyclohexene-d(10). These results suggest that a hydrogen atom abstraction from the allylic C-H bonds of olefins by a putative Mn-IV-superoxo species, which is formed by binding O-2 by a high-spin (S = 2) [Mn-III(TAML)](-) complex, is the rate-determining step. A Mn(V)-oxo complex binding Sc3+ ion, [Mn-V(O)(TAML)](-)-(Sc3+) (2), was also synthesized in the reaction of 1 with Sc3+ ion and then characterized using various spectroscopic techniques. The binding site of the Sc3+ ion was proposed to be the TAML ligand, not the Mn-O moiety, probably due to the low basicity of the oxo group compared to the basicity of the amide carbonyl group in the TAML ligand. Reactivity studies of the Mn(V)-oxo intermediates, 1 and 2, in oxygen atom transfer and electron-transfer reactions revealed that the binding of Sc3+ ion at the TAML ligand of Mn(V)-oxo enhanced its oxidizing power with a positively shifted one-electron reduction potential (Delta E-red = 0.70 V). This study reports the first example of tuning the second coordination sphere of high-valent metal-oxo species by binding a redox-inactive metal ion at the supporting ligand site, thereby modulating their electron-transfer properties as well as their reactivities in oxidation reactions. | * |
dc.language | English | * |
dc.publisher | AMER CHEMICAL SOC | * |
dc.title | A Manganese(V)-Oxo Complex: Synthesis by Dioxygen Activation and Enhancement of Its Oxidizing Power by Binding Scandium Ion | * |
dc.type | Article | * |
dc.relation.issue | 27 | * |
dc.relation.volume | 138 | * |
dc.relation.index | SCIE | * |
dc.relation.index | SCOPUS | * |
dc.relation.startpage | 8523 | * |
dc.relation.lastpage | 8532 | * |
dc.relation.journaltitle | JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | * |
dc.identifier.doi | 10.1021/jacs.6b03874 | * |
dc.identifier.wosid | WOS:000379794400036 | * |
dc.identifier.scopusid | 2-s2.0-84978771825 | * |
dc.author.google | Hong, Seungwoo | * |
dc.author.google | Lee, Yong-Min | * |
dc.author.google | Sankaralingam, Muniyandi | * |
dc.author.google | Vardhaman, Anil Kumar | * |
dc.author.google | Park, Young Jun | * |
dc.author.google | Cho, Kyung-Bin | * |
dc.author.google | Ogura, Takashi | * |
dc.author.google | Sarangi, Ritimukta | * |
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 | 이용민(36546331100;35233855500;57192113229) | * |
dc.date.modifydate | 20240401081001 | * |