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dc.contributor.author남원우*
dc.contributor.authorShunichi Fukuzumi*
dc.contributor.author이용민*
dc.date.accessioned2016-08-29T12:08:38Z-
dc.date.available2016-08-29T12:08:38Z-
dc.date.issued2016*
dc.identifier.issn0002-7863*
dc.identifier.otherOAK-19067*
dc.identifier.urihttps://dspace.ewha.ac.kr/handle/2015.oak/231756-
dc.description.abstractA 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.languageEnglish*
dc.publisherAMER CHEMICAL SOC*
dc.titleA Manganese(V)-Oxo Complex: Synthesis by Dioxygen Activation and Enhancement of Its Oxidizing Power by Binding Scandium Ion*
dc.typeArticle*
dc.relation.issue27*
dc.relation.volume138*
dc.relation.indexSCIE*
dc.relation.indexSCOPUS*
dc.relation.startpage8523*
dc.relation.lastpage8532*
dc.relation.journaltitleJOURNAL OF THE AMERICAN CHEMICAL SOCIETY*
dc.identifier.doi10.1021/jacs.6b03874*
dc.identifier.wosidWOS:000379794400036*
dc.identifier.scopusid2-s2.0-84978771825*
dc.author.googleHong, Seungwoo*
dc.author.googleLee, Yong-Min*
dc.author.googleSankaralingam, Muniyandi*
dc.author.googleVardhaman, Anil Kumar*
dc.author.googlePark, Young Jun*
dc.author.googleCho, Kyung-Bin*
dc.author.googleOgura, Takashi*
dc.author.googleSarangi, Ritimukta*
dc.author.googleFukuzumi, Shunichi*
dc.author.googleNam, Wonwoo*
dc.contributor.scopusid남원우(7006569723)-
dc.contributor.scopusidShunichi Fukuzumi(35430038100;57375583300)-
dc.contributor.scopusid이용민(36546331100;35233855500;57192113229)-
dc.date.modifydate20221001081001*
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자연과학대학 > 화학·나노과학전공 > Journal papers
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