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DC Field | Value | Language |
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dc.citation.endPage | 11392 | - |
dc.citation.number | 30 | - |
dc.citation.startPage | 11382 | - |
dc.citation.title | JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | - |
dc.citation.volume | 143 | - |
dc.contributor.author | Kim, Kyungmin | - |
dc.contributor.author | Cho, Dasol | - |
dc.contributor.author | Noh, Hyeonju | - |
dc.contributor.author | Ohta, Takehiro | - |
dc.contributor.author | Baik, Mu-Hyun | - |
dc.contributor.author | Cho, Jaeheung | - |
dc.date.accessioned | 2023-12-21T15:36:47Z | - |
dc.date.available | 2023-12-21T15:36:47Z | - |
dc.date.created | 2021-08-26 | - |
dc.date.issued | 2021-08 | - |
dc.description.abstract | Redox-inactive metal ions play vital roles in biological O-2 activation and oxidation reactions of various substrates. Recently, we showed a distinct reactivity of a peroxocobalt(III) complex bearing a tetradentate macrocyclic ligand, [Co-III(TBDAP)(O-2)](+) (1) (TBDAP = N,N'-di-tert-butyl-2,11-diaza[3.3](2,6)pyridinophane), toward nitriles that afforded a series of hydroximatocobalt(III) complexes, [Co-III(TBDAP)(R-C(=NO)O)](+) (R = Me (3), Et, and Ph). In this study, we report the effects of redox-inactive metal ions on nitrile activation of 1. In the presence of redox-inactive metal ions such as Zn2+, La3+, Lu3+, and Y3+, the reaction does not form the hydroximatocobalt(III) complex but instead gives peroxyimidatocobalt(III) complexes, [Co-III(TBDAP)(R-C(=NH)O-2)](2+) (R = Me (2) and Ph (2(Ph))). These new intermediates were characterized by various physicochemical methods including X-ray diffraction analysis. The rates of the formation of 2 are found to correlate with the Lewis acidity of the additive metal ions. Moreover, complex 2 was readily converted to 3 by the addition of a base. In the presence of Al3+, Sc3+, or H+, 1 is converted to [Co-III(TBDAP)(O2H)(MeCN)](2+) (4), and further reaction with nitriles did not occur. These results reveal that the reactivity of the peroxocobalt(III) complex 1 in nitrile activation can be regulated by the redox-inactive metal ions and their Lewis acidity. DFT calculations show that the redox-inactive metal ions stabilize the peroxo character of end-on Co-eta(1)-O-2 intermediate through the charge reorganization from a Co-II-superoxo to a Co-III-peroxo intermediate. A complete mechanistic model explaining the role of the Lewis acid is presented. | - |
dc.identifier.bibliographicCitation | JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, v.143, no.30, pp.11382 - 11392 | - |
dc.identifier.doi | 10.1021/jacs.1c01674 | - |
dc.identifier.issn | 0002-7863 | - |
dc.identifier.scopusid | 2-s2.0-85112719114 | - |
dc.identifier.uri | https://scholarworks.unist.ac.kr/handle/201301/55371 | - |
dc.identifier.url | https://pubs.acs.org/doi/10.1021/jacs.1c01674 | - |
dc.identifier.wosid | 000684586600014 | - |
dc.language | 영어 | - |
dc.publisher | AMER CHEMICAL SOC | - |
dc.title | Controlled Regulation of the Nitrile Activation of a Peroxocobalt(III) Complex with Redox-Inactive Lewis Acidic Metals | - |
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 | MOLECULAR-ORBITAL METHODS | - |
dc.subject.keywordPlus | GAUSSIAN-TYPE BASIS | - |
dc.subject.keywordPlus | EFFECTIVE CORE POTENTIALS | - |
dc.subject.keywordPlus | ELECTRON-TRANSFER REACTIONS | - |
dc.subject.keywordPlus | HYDRIDE-TRANSFER REACTIONS | - |
dc.subject.keywordPlus | OXYGEN-EVOLVING COMPLEX | - |
dc.subject.keywordPlus | SOLVATION FREE-ENERGIES | - |
dc.subject.keywordPlus | BASIS-SETS | - |
dc.subject.keywordPlus | QUANTITATIVE-EVALUATION | - |
dc.subject.keywordPlus | OXIDATION REACTIONS | - |
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