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dc.contributor.author남원우-
dc.contributor.authorShunichi Fukuzumi-
dc.date.accessioned2020-02-11T16:30:05Z-
dc.date.available2020-02-11T16:30:05Z-
dc.date.issued2020-
dc.identifier.issn0002-7863-
dc.identifier.issn1520-5126-
dc.identifier.otherOAK-26472-
dc.identifier.urihttp://dspace.ewha.ac.kr/handle/2015.oak/253401-
dc.description.abstractCalcium ion plays an indispensable role for water oxidation by oxygen-evolving complex (OEC) composed of a manganese-oxo cluster (Mn4CaO5) in Photosystem II. In this context, the effects of Ca2+ ion and other redox-inactive metal ions on the redox reactivity of high-valent metal-oxo and metal-peroxo complexes have been studied extensively. Among metal-oxygen intermediates involved in interconversion between H2O and O-2, however, the effects of Ca2+ ion and other redox-inactive metal ions (Mn+) on the redox reactivity of metal-superoxo complexes have yet to be reported. Herein, we report that electron transfer (ET) from octamethylferrocene (Me(8)Fc) to a mononuclear nonheme Cr(III)-superoxo complex, [(Cl)(TMC)Cr-III(O-2)]+ (1), occurs in the presence of redox-inactive metal ions (Mn+ = Ca2+, Mg2+, Y3+, Al3+, and Sc3+); in the absence of the redox-inactive metal ions, ET from Me(8)Fc to 1 does not occur. The secondorder rate constants (k(et)) of ET from Me(8)Fc to 1 in the presence of a redox-inactive metal ion increased with increasing concentration of Mn+ ([Mn+]), exhibiting a second-order dependence on [Mn+]: k(et) = k(MCET)[Mn+2](2), where k(MCET) is the fourthorder rate constant of metal ion-coupled electron transfer (MCET). This means that two Mn+ ions are bound to the oneelectron reduced species of 1. Such a binding of two Mn+ ons associated with the ET reduction of! resulted in a 92 mV positive shift of the one-electron reduction potential of 1 (E-red) with increasing log( [Mn+]). The log kmcET values increased linearly with the increasing Lewis acidity of Mn+ (Delta E), which was determined from the g values of O-2(center dot-)-Mn+ complexes. The driving force dependence of log k(et) of MCET from ferrocene derivatives to 1 in the presence of Mn+ has been well-evaluated in light of the Marcus theory of electron transfer.-
dc.languageEnglish-
dc.publisherAMER CHEMICAL SOC-
dc.titleTuning Electron-Transfer Reactivity of a Chromium(III)-Superoxo Complex Enabled by Calcium Ion and Other Redox-Inactive Metal Ions-
dc.typeArticle-
dc.relation.issue1-
dc.relation.volume142-
dc.relation.indexSCI-
dc.relation.indexSCIE-
dc.relation.indexSCOPUS-
dc.relation.startpage365-
dc.relation.lastpage372-
dc.relation.journaltitleJOURNAL OF THE AMERICAN CHEMICAL SOCIETY-
dc.identifier.doi10.1021/jacs.9b11014-
dc.identifier.wosidWOS:000507144400047-
dc.author.googleDevi, Tarali-
dc.author.googleLee, Yong-Min-
dc.author.googleNam, Wonwoo-
dc.author.googleFukuzumi, Shunichi-
dc.contributor.scopusid남원우(7006569723)-
dc.contributor.scopusidShunichi Fukuzumi(35430038100)-
dc.date.modifydate20200403081004-
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자연과학대학 > 화학·나노과학전공 > Journal papers
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