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DC Field | Value | Language |
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dc.citation.endPage | 16986 | - |
dc.citation.number | 47 | - |
dc.citation.startPage | 16977 | - |
dc.citation.title | JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | - |
dc.citation.volume | 132 | - |
dc.contributor.author | Cho, Jaeheung | - |
dc.contributor.author | Sarangi, Ritimukta | - |
dc.contributor.author | Kang, Hye Yeon | - |
dc.contributor.author | Lee, Jung Yoon | - |
dc.contributor.author | Kubo, Minoru | - |
dc.contributor.author | Ogura, Takashi | - |
dc.contributor.author | Solomon, Edward I. | - |
dc.contributor.author | Nam, Wonwoo | - |
dc.date.accessioned | 2023-12-22T06:38:15Z | - |
dc.date.available | 2023-12-22T06:38:15Z | - |
dc.date.created | 2020-09-01 | - |
dc.date.issued | 2010-12 | - |
dc.description.abstract | Metal−dioxygen adducts are key intermediates detected in the catalytic cycles of dioxygen activation by metalloenzymes and biomimetic compounds. In this study, mononuclear cobalt(III)−peroxo complexes bearing tetraazamacrocyclic ligands, [Co(12-TMC)(O2)]+ and [Co(13-TMC)(O2)]+, were synthesized by reacting [Co(12-TMC)(CH3CN)]2+ and [Co(13-TMC)(CH3CN)]2+, respectively, with H2O2 in the presence of triethylamine. The mononuclear cobalt(III)−peroxo intermediates were isolated and characterized by various spectroscopic techniques and X-ray crystallography, and the structural and spectroscopic characterization demonstrated unambiguously that the peroxo ligand is bound in a side-on η2 fashion. The O−O bond stretching frequency of [Co(12-TMC)(O2)]+ and [Co(13-TMC)(O2)]+ was determined to be 902 cm−1 by resonance Raman spectroscopy. The structural properties of the CoO2 core in both complexes are nearly identical; the O−O bond distances of [Co(12-TMC)(O2)]+ and [Co(13-TMC)(O2)]+ were 1.4389(17) Å and 1.438(6) Å, respectively. The cobalt(III)−peroxo complexes showed reactivities in the oxidation of aldehydes and O2-transfer reactions. In the aldehyde oxidation reactions, the nucleophilic reactivity of the cobalt−peroxo complexes was significantly dependent on the ring size of the macrocyclic ligands, with the reactivity of [Co(13-TMC)(O2)]+ > [Co(12-TMC)(O2)]+. In the O2-transfer reactions, the cobalt(III)−peroxo complexes transferred the bound peroxo group to a manganese(II) complex, affording the corresponding cobalt(II) and manganese(III)−peroxo complexes. The reactivity of the cobalt−peroxo complexes in O2-transfer was also significantly dependent on the ring size of tetraazamacrocycles, and the reactivity order in the O2-transfer reactions was the same as that observed in the aldehyde oxidation reactions. | - |
dc.identifier.bibliographicCitation | JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, v.132, no.47, pp.16977 - 16986 | - |
dc.identifier.doi | 10.1021/ja107177m | - |
dc.identifier.issn | 0002-7863 | - |
dc.identifier.scopusid | 2-s2.0-78649526666 | - |
dc.identifier.uri | https://scholarworks.unist.ac.kr/handle/201301/48146 | - |
dc.identifier.url | https://pubs.acs.org/doi/10.1021/ja107177m | - |
dc.identifier.wosid | 000284972400041 | - |
dc.language | 영어 | - |
dc.publisher | AMER CHEMICAL SOC | - |
dc.title | Synthesis, Structural, and Spectroscopic Characterization and Reactivities of Mononuclear Cobalt(III)-Peroxo Complexes | - |
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.keywordPlus | ABSORPTION FINE-STRUCTURE | - |
dc.subject.keywordPlus | ALPHA-HYDROXYLATING MONOOXYGENASE | - |
dc.subject.keywordPlus | COPPER-DIOXYGEN ADDUCT | - |
dc.subject.keywordPlus | GAUSSIAN-BASIS SETS | - |
dc.subject.keywordPlus | D-BETA-M | - |
dc.subject.keywordPlus | END-ON | - |
dc.subject.keywordPlus | MOLECULAR-OXYGEN | - |
dc.subject.keywordPlus | METAL-COMPLEXES | - |
dc.subject.keywordPlus | PORPHYRIN COMPLEXES | - |
dc.subject.keywordPlus | SUPEROXO COMPLEX | - |
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