Full metadata record
DC Field | Value | Language |
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dc.contributor.author | Lee, Yong-Min | - |
dc.contributor.author | Bang, Suhee | - |
dc.contributor.author | Kim, Yun Mi | - |
dc.contributor.author | Cho, Jaeheung | - |
dc.contributor.author | Hong, Seungwoo | - |
dc.contributor.author | Nomura, Takashi | - |
dc.contributor.author | Ogura, Takashi | - |
dc.contributor.author | Troeppner, Oliver | - |
dc.contributor.author | Ivanovic-Burmazovic, Ivana | - |
dc.contributor.author | Sarangi, Ritimukta | - |
dc.contributor.author | Fukuzumi, Shunichi | - |
dc.contributor.author | Nam, Wonwoo | - |
dc.date.available | 2017-07-11T06:41:20Z | - |
dc.date.created | 2017-04-10 | - |
dc.date.issued | 2013-10 | - |
dc.identifier.issn | 2041-6520 | - |
dc.identifier.uri | http://hdl.handle.net/20.500.11750/3298 | - |
dc.description.abstract | Redox-inactive metal ions that function as Lewis acids play pivotal roles in modulating reactivities of oxygen-containing metal complexes in a variety of biological and biomimetic reactions, including dioxygen activation/formation and functionalization of organic substrates. Mononuclear nonheme iron(iii)-peroxo species are invoked as active oxygen intermediates in the catalytic cycles of dioxygen activation by nonheme iron enzymes and their biomimetic compounds. Here, we report mononuclear nonheme iron(iii)-peroxo complexes binding redox-inactive metal ions, [(TMC)FeIII(O2)] +-M3+ (M3+ = Sc3+ and Y 3+; TMC = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane), which are characterized spectroscopically as a 'side-on' iron(iii)-peroxo complex binding a redox-inactive metal ion, (TMC)FeIII-(μ, η2:η2-O2)-M3+ (2-M). While an iron(iii)-peroxo complex, [(TMC)FeIII(O2)]+, does not react with electron donors (e.g., ferrocene), one-electron reduction of the iron(iii)-peroxo complexes binding redox-inactive metal ions occurs readily upon addition of electron donors, resulting in the generation of an iron(iv)-oxo complex, [(TMC)FeIV(O)]2+ (4), via heterolytic O-O bond cleavage of the peroxide ligand. The rates of the conversion of 2-M to 4 are found to depend on the Lewis acidity of the redox-inactive metal ions and the oxidation potential of the electron donors. We have also determined the fundamental electron-transfer properties of 2-M, such as the reduction potential and the reorganization energy in electron-transfer reaction. Based on the results presented herein, we have proposed a mechanism for the reactions of 2-M and electron donors; the reduction of 2-M to the reduced species, (TMC)FeII-(O2)-M3+ (2′-M), is the rate-determining step, followed by heterolytic O-O bond cleavage of the reduced species to form 4. The present results provide a biomimetic example demonstrating that redox-inactive metal ions bound to an iron(iii)-peroxo intermediate play a significant role in activating the peroxide O-O bond to form a high-valent iron(iv)-oxo species. © 2013 The Royal Society of Chemistry. | - |
dc.language | English | - |
dc.publisher | Royal Society of Chemistry | - |
dc.title | A mononuclear nonheme iron(III)-peroxo complex binding redox-inactive metal ions | - |
dc.type | Article | - |
dc.identifier.doi | 10.1039/c3sc51864g | - |
dc.identifier.scopusid | 2-s2.0-84883308619 | - |
dc.identifier.bibliographicCitation | Chemical Science, v.4, no.10, pp.3917 - 3923 | - |
dc.description.isOpenAccess | FALSE | - |
dc.subject.keywordPlus | COUPLED ELECTRON-TRANSFER | - |
dc.subject.keywordPlus | CYTOCHROME-C-OXIDASE | - |
dc.subject.keywordPlus | OXYGEN-EVOLVING COMPLEX | - |
dc.subject.keywordPlus | CRYSTAL-STRUCTURE | - |
dc.subject.keywordPlus | IRON OXYGENASES | - |
dc.subject.keywordPlus | PHOTOSYSTEM-II | - |
dc.subject.keywordPlus | LEWIS ACIDITY | - |
dc.subject.keywordPlus | ATOM TRANSFER | - |
dc.subject.keywordPlus | ACTIVATION | - |
dc.subject.keywordPlus | INTERMEDIATE | - |
dc.citation.endPage | 3923 | - |
dc.citation.number | 10 | - |
dc.citation.startPage | 3917 | - |
dc.citation.title | Chemical Science | - |
dc.citation.volume | 4 | - |
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