DC Field | Value | Language |
---|---|---|
dc.contributor.author | Kojima, T | - |
dc.contributor.author | Hayashi, KI | - |
dc.contributor.author | Iizuka, SY | - |
dc.contributor.author | Tani, F | - |
dc.contributor.author | Naruta, Y | - |
dc.contributor.author | Kawano, M | - |
dc.contributor.author | Yuji Ohashi | - |
dc.contributor.author | Hirai, Y | - |
dc.contributor.author | Ohkubold, K | - |
dc.contributor.author | Matsuda, Y | - |
dc.contributor.author | Fukuzumi, S | - |
dc.date.accessioned | 2016-04-01T02:56:46Z | - |
dc.date.available | 2016-04-01T02:56:46Z | - |
dc.date.created | 2010-12-07 | - |
dc.date.issued | 2007-01 | - |
dc.identifier.issn | 0947-6539 | - |
dc.identifier.other | 2010-OAK-0000021080 | - |
dc.identifier.uri | https://oasis.postech.ac.kr/handle/2014.oak/26026 | - |
dc.description.abstract | A series of mononuclear Ru-III complexes [RuCl2(L)](+), where L is tris(2-pyridylmethyl)amine (TPA) or one of four TPA derivatives as tetradentate ligand, were prepared and characterized by spectroscopic methods, X-ray crystallography, and electrochemical measurements. The geometry of a Ru-III complex having a non-threefold-symmetric TPA ligand bearing one dimethylnicotinamide moiety was determined to show that the nicotine moiety resides trans to a pyridine group, but not to the chlorido ligand. The substituents of the TPA ligands were shown to regulate the redox potential of the ruthenium center, as indicated by a linear Hammett plot in the range of 200 mV for Ru-III/Ru-IV couples with a relatively large p value (+ 0.150). These complexes act as effective catalysts for alkane functionalization in acetonitrile with m-chloroperbenzoic acid (mCPBA) as terminal oxidant at room temperature. They exhibited fairly good reactivity for oxidation of cyclohexane (C-H bond energy 94 kcalmol(-1)), and the reactivity can be altered significantly by the electronic effects of substituents on TPA ligands in terms of initial rates and turn-over numbers. Catalytic oxygenation of cyclohexane by a Ru-III complex with O-16-mCPBA in the presence of (H2O)-O-18 gave O-18-labeled cyclohexanol with 100% inclusion of the O-18 atom from the water molecule. Resonance Raman spectra under catalytic conditions without the substrate indicate formation of a Ru-IV=O intermediate with lower bonding energy. Kinetic isotope effects (KIEs) in the oxidation of cyclohexane suggest that hydrogen abstraction is the rate-determining step and the KIE values depend on the substituents of the TPA ligands. Thus, the reaction mechanism of catalytic cyclohexane oxygenation depends on the electronic effects of the ligands. | - |
dc.description.statementofresponsibility | X | - |
dc.language | English | - |
dc.publisher | WILEY-V C H VERLAG GMBH | - |
dc.relation.isPartOf | CHEMISTRY-A EUROPEAN JOURNAL | - |
dc.subject | N ligands | - |
dc.subject | oxygenation reaction | - |
dc.subject | mechanisms | - |
dc.subject | redox chemistry | - |
dc.subject | ruthenium | - |
dc.subject | ISOTOPICALLY LABELED WATER | - |
dc.subject | HINDERED RUTHENIUM COMPLEX | - |
dc.subject | NONHEME IRON CATALYST | - |
dc.subject | RAY CRYSTAL-STRUCTURE | - |
dc.subject | METHANE MONOOXYGENASE | - |
dc.subject | DIOXYGEN ACTIVATION | - |
dc.subject | CIS-DIHYDROXYLATION | - |
dc.subject | MOLECULAR-OXYGEN | - |
dc.subject | HYDROCARBON OXYGENATION | - |
dc.subject | PORPHYRIN COMPLEX | - |
dc.title | Synthesis and characterization of mononuclear Ruthenium(III)Pyridylamine complexes and mechanistic insights into their catalytic alkane functionalization with m-chloroperbenzoic acid | - |
dc.type | Article | - |
dc.contributor.college | 첨단재료과학부 | - |
dc.identifier.doi | 10.1002/CHEM.200700190 | - |
dc.author.google | Kojima, T | - |
dc.author.google | Hayashi, KI | - |
dc.author.google | Iizuka, SY | - |
dc.author.google | Tani, F | - |
dc.author.google | Naruta, Y | - |
dc.author.google | Kawano, M | - |
dc.author.google | Ohashi, Y | - |
dc.author.google | Hirai, Y | - |
dc.author.google | Ohkubold, K | - |
dc.author.google | Matsuda, Y | - |
dc.author.google | Fukuzumi, S | - |
dc.relation.volume | 13 | - |
dc.relation.issue | 29 | - |
dc.relation.startpage | 8212 | - |
dc.relation.lastpage | 8222 | - |
dc.contributor.id | 10648581 | - |
dc.relation.journal | CHEMISTRY-A EUROPEAN JOURNAL | - |
dc.relation.index | SCI급, SCOPUS 등재논문 | - |
dc.relation.sci | SCI | - |
dc.collections.name | Journal Papers | - |
dc.type.rims | ART | - |
dc.identifier.bibliographicCitation | CHEMISTRY-A EUROPEAN JOURNAL, v.13, no.29, pp.8212 - 8222 | - |
dc.identifier.wosid | 000250253400013 | - |
dc.date.tcdate | 2019-02-01 | - |
dc.citation.endPage | 8222 | - |
dc.citation.number | 29 | - |
dc.citation.startPage | 8212 | - |
dc.citation.title | CHEMISTRY-A EUROPEAN JOURNAL | - |
dc.citation.volume | 13 | - |
dc.contributor.affiliatedAuthor | Kawano, M | - |
dc.identifier.scopusid | 2-s2.0-35349009589 | - |
dc.description.journalClass | 1 | - |
dc.description.journalClass | 1 | - |
dc.description.wostc | 28 | - |
dc.description.scptc | 23 | * |
dc.date.scptcdate | 2018-05-121 | * |
dc.type.docType | Article | - |
dc.subject.keywordPlus | ISOTOPICALLY LABELED WATER | - |
dc.subject.keywordPlus | HINDERED RUTHENIUM COMPLEX | - |
dc.subject.keywordPlus | NONHEME IRON CATALYST | - |
dc.subject.keywordPlus | RAY CRYSTAL-STRUCTURE | - |
dc.subject.keywordPlus | METHANE MONOOXYGENASE | - |
dc.subject.keywordPlus | DIOXYGEN ACTIVATION | - |
dc.subject.keywordPlus | CIS-DIHYDROXYLATION | - |
dc.subject.keywordPlus | MOLECULAR-OXYGEN | - |
dc.subject.keywordPlus | HYDROCARBON OXYGENATION | - |
dc.subject.keywordPlus | PORPHYRIN COMPLEX | - |
dc.subject.keywordAuthor | N ligands | - |
dc.subject.keywordAuthor | oxygenation reaction | - |
dc.subject.keywordAuthor | mechanisms | - |
dc.subject.keywordAuthor | redox chemistry | - |
dc.subject.keywordAuthor | ruthenium | - |
dc.relation.journalWebOfScienceCategory | Chemistry, Multidisciplinary | - |
dc.description.journalRegisteredClass | scie | - |
dc.description.journalRegisteredClass | scopus | - |
dc.relation.journalResearchArea | Chemistry | - |
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