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분자활성 촉매반응 연구단
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Controlled Regulation of the Nitrile Activation of a Peroxocobalt(III) Complex with Redox-Inactive Lewis Acidic Metals

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dc.contributor.authorKim, Kyungmin-
dc.contributor.authorDasol Cho-
dc.contributor.authorNoh, Hyeonju-
dc.contributor.authorOhta, Takehiro-
dc.contributor.authorMu-Hyun Baik-
dc.contributor.authorCho, Jaeheung-
dc.date.accessioned2021-11-04T01:50:04Z-
dc.date.available2021-11-04T01:50:04Z-
dc.date.created2021-11-01-
dc.date.issued2021-08-04-
dc.identifier.issn0002-7863-
dc.identifier.urihttps://pr.ibs.re.kr/handle/8788114/10587-
dc.description.abstractRedox-inactive metal ions play vital roles in biological O2 activation and oxidation reactions of various substrates. Recently, we showed a distinct reactivity of a peroxocobalt(III) complex bearing a tetradentate macrocyclic ligand, [CoIII(TBDAP)(O2)]+ (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, [CoIII(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, [CoIII(TBDAP)(R-C(NH)O2)]2+ (R = Me (2) and Ph (2Ph)). 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 [CoIII(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-η1-O2 intermediate through the charge reorganization from a CoII-superoxo to a CoIII-peroxo intermediate. A complete mechanistic model explaining the role of the Lewis acid is presented.-
dc.language영어-
dc.publisherAmerican Chemical Society-
dc.titleControlled Regulation of the Nitrile Activation of a Peroxocobalt(III) Complex with Redox-Inactive Lewis Acidic Metals-
dc.typeArticle-
dc.type.rimsART-
dc.identifier.wosid000684586600014-
dc.identifier.scopusid2-s2.0-85112719114-
dc.identifier.rimsid76527-
dc.contributor.affiliatedAuthorDasol Cho-
dc.contributor.affiliatedAuthorMu-Hyun Baik-
dc.identifier.doi10.1021/jacs.1c01674-
dc.identifier.bibliographicCitationJournal of the American Chemical Society, v.143, no.30, pp.11382 - 11392-
dc.relation.isPartOfJournal of the American Chemical Society-
dc.citation.titleJournal of the American Chemical Society-
dc.citation.volume143-
dc.citation.number30-
dc.citation.startPage11382-
dc.citation.endPage11392-
dc.type.docTypeArticle-
dc.description.journalClass1-
dc.description.journalClass1-
dc.description.isOpenAccessN-
dc.description.journalRegisteredClassscie-
dc.description.journalRegisteredClassscopus-
dc.relation.journalResearchAreaChemistry-
dc.relation.journalWebOfScienceCategoryChemistry, Multidisciplinary-
dc.subject.keywordPlusMOLECULAR-ORBITAL METHODS-
dc.subject.keywordPlusGAUSSIAN-TYPE BASIS-
dc.subject.keywordPlusEFFECTIVE CORE POTENTIALS-
dc.subject.keywordPlusELECTRON-TRANSFER REACTIONS-
dc.subject.keywordPlusHYDRIDE-TRANSFER REACTIONS-
dc.subject.keywordPlusOXYGEN-EVOLVING COMPLEX-
dc.subject.keywordPlusSOLVATION FREE-ENERGIES-
dc.subject.keywordPlusBASIS-SETS-
dc.subject.keywordPlusQUANTITATIVE-EVALUATION-
dc.subject.keywordPlusOXIDATION REACTIONS-
Appears in Collections:
Center for Catalytic Hydrocarbon Functionalizations(분자활성 촉매반응 연구단) > 1. Journal Papers (저널논문)
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