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DC Field | Value | Language |
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dc.citation.endPage | 1093 | - |
dc.citation.number | 4 | - |
dc.citation.startPage | 1084 | - |
dc.citation.title | CHEMISTRY-A EUROPEAN JOURNAL | - |
dc.citation.volume | 18 | - |
dc.contributor.author | Tahsini, Laleh | - |
dc.contributor.author | Kotani, Hiroaki | - |
dc.contributor.author | Lee, Yong-Min | - |
dc.contributor.author | Cho, Jaeheung | - |
dc.contributor.author | Nam, Wonwoo | - |
dc.contributor.author | Karlin, Kenneth D. | - |
dc.contributor.author | Fukuzumi, Shunichi | - |
dc.date.accessioned | 2023-12-22T05:36:30Z | - |
dc.date.available | 2023-12-22T05:36:30Z | - |
dc.date.created | 2020-09-01 | - |
dc.date.issued | 2012-01 | - |
dc.description.abstract | The four‐electron reduction of dioxygen by decamethylferrocene (Fc*) to water is efficiently catalyzed by a binuclear copper(II) complex (1) and a mononuclear copper(II) complex (2) in the presence of trifluoroacetic acid in acetone at 298 K. Fast electron transfer from Fc* to 1 and 2 affords the corresponding CuI complexes, which react at low temperature (193 K) with dioxygen to afford the η2:η2‐peroxo dicopper(II) (3) and bis‐μ‐oxo dicopper(III) (4) intermediates, respectively. The rate constants for electron transfer from Fc* and octamethylferrocene (Me8Fc) to 1 as well as electron transfer from Fc* and Me8Fc to 3 were determined at various temperatures, leading to activation enthalpies and entropies. The activation entropies of electron transfer from Fc* and Me8Fc to 1 were determined to be close to zero, as expected for outer‐sphere electron‐transfer reactions without formation of any intermediates. For electron transfer from Fc* and Me8Fc to 3, the activation entropies were also found to be close to zero. Such agreement indicates that the η2:η2‐peroxo complex (3) is directly reduced by Fc* rather than via the conversion to the corresponding bis‐μ‐oxo complex, followed by the electron‐transfer reduction by Fc* leading to the four‐electron reduction of dioxygen to water. The bis‐μ‐oxo species (4) is reduced by Fc* with a much faster rate than the η2:η2‐peroxo complex (3), but this also leads to the four‐electron reduction of dioxygen to water. | - |
dc.identifier.bibliographicCitation | CHEMISTRY-A EUROPEAN JOURNAL, v.18, no.4, pp.1084 - 1093 | - |
dc.identifier.doi | 10.1002/chem.201103215 | - |
dc.identifier.issn | 0947-6539 | - |
dc.identifier.scopusid | 2-s2.0-84862941189 | - |
dc.identifier.uri | https://scholarworks.unist.ac.kr/handle/201301/48136 | - |
dc.identifier.url | https://chemistry-europe.onlinelibrary.wiley.com/doi/full/10.1002/chem.201103215 | - |
dc.identifier.wosid | 000299075600012 | - |
dc.language | 영어 | - |
dc.publisher | WILEY-V C H VERLAG GMBH | - |
dc.title | Electron-Transfer Reduction of Dinuclear Copper Peroxo and Bis-mu-oxo Complexes Leading to the Catalytic Four-Electron Reduction of Dioxygen to Water | - |
dc.type | Article | - |
dc.description.isOpenAccess | FALSE | - |
dc.relation.journalWebOfScienceCategory | Chemistry, Multidisciplinary | - |
dc.relation.journalResearchArea | Chemistry | - |
dc.type.docType | Article | - |
dc.description.journalRegisteredClass | scie | - |
dc.description.journalRegisteredClass | scopus | - |
dc.subject.keywordAuthor | copper | - |
dc.subject.keywordAuthor | dioxygen | - |
dc.subject.keywordAuthor | electron transfer | - |
dc.subject.keywordAuthor | ferrocene | - |
dc.subject.keywordAuthor | oxygen reduction reaction | - |
dc.subject.keywordPlus | CYTOCHROME-C-OXIDASE | - |
dc.subject.keywordPlus | NONHEME OXOIRON(IV) COMPLEXES | - |
dc.subject.keywordPlus | COFACIAL DICOBALT PORPHYRINS | - |
dc.subject.keywordPlus | NADH MODEL-COMPOUND | - |
dc.subject.keywordPlus | O-O BOND | - |
dc.subject.keywordPlus | PERCHLORIC-ACID | - |
dc.subject.keywordPlus | FERROCENE DERIVATIVES | - |
dc.subject.keywordPlus | DICOPPER(I) COMPLEXES | - |
dc.subject.keywordPlus | MULTICOPPER OXIDASES | - |
dc.subject.keywordPlus | MECHANISTIC INSIGHTS | - |
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