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DC Field | Value | Language |
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dc.citation.endPage | 13108 | - |
dc.citation.number | 50 | - |
dc.citation.startPage | 13102 | - |
dc.citation.title | JOURNAL OF PHYSICAL CHEMISTRY A | - |
dc.citation.volume | 112 | - |
dc.contributor.author | Kamachi, Takashi | - |
dc.contributor.author | Lee, Yong-Min | - |
dc.contributor.author | Nishimi, Tomonori | - |
dc.contributor.author | Cho, Jaeheung | - |
dc.contributor.author | Yoshizawa, Kazunari | - |
dc.contributor.author | Nam, Wonwoo | - |
dc.date.accessioned | 2023-12-22T08:13:12Z | - |
dc.date.available | 2023-12-22T08:13:12Z | - |
dc.date.created | 2020-09-01 | - |
dc.date.issued | 2008-12 | - |
dc.description.abstract | A copper(II) complex bearing a pentadentate ligand, [Cu-II(N4Py)(CF3SO3)(2)] (1) (N4Py = N,N-bis(2pyridylmethyl)bis(2-pyridyl)methylamine) was synthesized and characterized with various spectroscopic techniques and X-ray crystallography. A mononuclear Cu-II-hydroperoxo complex, [Cu-II(N4Py)(OOH)](+) (2), was then generated in the reaction of 1 and H2O2 in the presence of base, and the reactivity of the intermediate was investigated in the oxidation of various substrates at -40 degrees C. In the reactivity studies, 2 showed a low oxidizing power such that 2 reacted only with triethylphosphine but not with other substrates such as thioanisole, benzyl alcohol, 1,4-cyclohexadiene, cyclohexene, and cyclohexane. In theoretical work, we have conducted density functional theory (DFT) calculations on the epoxidation of ethylene by 2 and a [Cu-III(N4Py)(O)](+) intermediate (3) at the B3LYP level. The activation barrier is calculated to be 39.7 and 26.3 kcal/mol for distal and proximal oxygen attacks by 2, respectively. This result indicates that the direct ethylene epoxidation by 2 is not a plausible pathway, as we have observed in the experimental work. In contrast, the ethylene epoxidation by 3 is a downhill and low-barrier process. We also found that 2 cannot be a precursor to 3, since the homolytic cleavage of the O-O bond of 2 is very endothermic (i.e., 42 kcal/mol). On the basis of the experimental and theoretical results, we conclude that a mononuclear Cu-II-hydroperoxo species bearing a pentadentate N5 ligand is a sluggish oxidant in oxygenation reactions. | - |
dc.identifier.bibliographicCitation | JOURNAL OF PHYSICAL CHEMISTRY A, v.112, no.50, pp.13102 - 13108 | - |
dc.identifier.doi | 10.1021/jp804804j | - |
dc.identifier.issn | 1089-5639 | - |
dc.identifier.scopusid | 2-s2.0-58149164877 | - |
dc.identifier.uri | https://scholarworks.unist.ac.kr/handle/201301/48155 | - |
dc.identifier.url | https://pubs.acs.org/doi/10.1021/jp804804j | - |
dc.identifier.wosid | 000261652800047 | - |
dc.language | 영어 | - |
dc.publisher | AMER CHEMICAL SOC | - |
dc.title | Combined Experimental and Theoretical Approach To Understand the Reactivity of a Mononuclear Cu(II)-Hydroperoxo Complex in Oxygenation Reactions | - |
dc.type | Article | - |
dc.description.isOpenAccess | FALSE | - |
dc.relation.journalWebOfScienceCategory | Chemistry, Physical; Physics, Atomic, Molecular & Chemical | - |
dc.relation.journalResearchArea | Chemistry; Physics | - |
dc.type.docType | Article | - |
dc.description.journalRegisteredClass | scie | - |
dc.description.journalRegisteredClass | scopus | - |
dc.subject.keywordPlus | DOPAMINE BETA-MONOOXYGENASE | - |
dc.subject.keywordPlus | ALPHA-HYDROXYLATING MONOOXYGENASE | - |
dc.subject.keywordPlus | MOLECULAR-ORBITAL METHODS | - |
dc.subject.keywordPlus | COPPER-DIOXYGEN ADDUCT | - |
dc.subject.keywordPlus | GAUSSIAN-TYPE BASIS | - |
dc.subject.keywordPlus | CATALYTIC MECHANISM | - |
dc.subject.keywordPlus | END-ON | - |
dc.subject.keywordPlus | HYDROPEROXO-COPPER(II) COMPLEX | - |
dc.subject.keywordPlus | CHEMICAL MECHANISM | - |
dc.subject.keywordPlus | ORGANIC-MOLECULES | - |
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