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DC Field | Value | Language |
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dc.citation.endPage | 7149 | - |
dc.citation.number | 19 | - |
dc.citation.startPage | 7141 | - |
dc.citation.title | INORGANIC CHEMISTRY | - |
dc.citation.volume | 62 | - |
dc.contributor.author | Kim, Kyungmin | - |
dc.contributor.author | Oh, Seongmin | - |
dc.contributor.author | Jeong, Donghyun | - |
dc.contributor.author | Lee, Yuri | - |
dc.contributor.author | Moon, Dohyun | - |
dc.contributor.author | Lee, Sunggi | - |
dc.contributor.author | Cho, Jaeheung | - |
dc.date.accessioned | 2023-12-21T12:38:58Z | - |
dc.date.available | 2023-12-21T12:38:58Z | - |
dc.date.created | 2023-06-15 | - |
dc.date.issued | 2023-05 | - |
dc.description.abstract | A series of cobalt(III)-peroxo complexes, [Co-III(R-2-TBDAP)(O-2)](+) (1(R2); R2 = Cl, H, and OMe), and cobalt(III)-hydroperoxo complexes, [CoIII(R2-TBDAP)(O2H)-(CH3CN)]2+ (2R2), bearing electronically tuned tetraazamacrocyclic ligands (R2-TBDAP = N,N'-di-tert-butyl-2,11-diaza[3.3](2,6)-p-R2-pyridinophane) were prepared from their cobalt(II) precursors and characterized by various physicochemical methods. The X-ray diffraction and spectroscopic analyses unambiguously showed that all 1R2 compounds have similar octahedral geometry with a side-on peroxocobalt(III) moiety, but the O-O bond lengths of 1Cl [1.398(3) A] and 1OMe [1.401(4) A] were shorter than that of 1H [1.456(3) A] due to the different spin states. For 2R2, the O-O bond vibration energies of 2Cl and 2OMe were identical at 853 cm-1 (856 cm-1 for 2H), but their Co-O bond vibration frequencies were observed at 572 cm-1 for 2Cl and 550 cm-1 for 2OMe, respectively, by resonance Raman spectroscopy (560 cm-1 for 2H). Interestingly, the redox potentials (E1/2) of 2R2 increased in the order of 2OMe (0.19 V) < 2H (0.24 V) < 2Cl (0.34 V) according to the electron richness of the R2-TBDAP ligands, but the oxygen-atom-transfer reactivities of 2R2 showed a reverse trend (k2: 2Cl < 2H < 2OMe) with a 13-fold rate enhancement at 2OMe over 2Cl in a sulfoxidation reaction with thioanisole. Although the reactivity trend contradicts the general consideration that electron-rich metal-oxygen species with low E1/2 values have sluggish electrophilic reactivity, this could be explained by a weak Co-O bond vibration of 2OMe in the unusual reaction pathway. These results provide considerable insight into the electronic nature-reactivity relationship of metal-oxygen species. | - |
dc.identifier.bibliographicCitation | INORGANIC CHEMISTRY, v.62, no.19, pp.7141 - 7149 | - |
dc.identifier.doi | 10.1021/acs.inorgchem.3c00826 | - |
dc.identifier.issn | 0020-1669 | - |
dc.identifier.scopusid | 2-s2.0-85159591785 | - |
dc.identifier.uri | https://scholarworks.unist.ac.kr/handle/201301/64484 | - |
dc.identifier.wosid | 000991428800001 | - |
dc.language | 영어 | - |
dc.publisher | AMER CHEMICAL SOC | - |
dc.title | Systematic Electronic Tuning on the Property and Reactivity of Cobalt-(Hydro)peroxo Intermediates | - |
dc.type | Article | - |
dc.description.isOpenAccess | FALSE | - |
dc.relation.journalWebOfScienceCategory | Chemistry, Inorganic & Nuclear | - |
dc.relation.journalResearchArea | Chemistry | - |
dc.type.docType | Article; Early Access | - |
dc.description.journalRegisteredClass | scie | - |
dc.description.journalRegisteredClass | scopus | - |
dc.subject.keywordPlus | ATOM TRANSFER | - |
dc.subject.keywordPlus | O-O | - |
dc.subject.keywordPlus | STRUCTURAL-CHARACTERIZATION | - |
dc.subject.keywordPlus | NUCLEOPHILIC REACTIVITY | - |
dc.subject.keywordPlus | ACTIVATED BLEOMYCIN | - |
dc.subject.keywordPlus | AXIAL LIGAND | - |
dc.subject.keywordPlus | HIGH-SPIN | - |
dc.subject.keywordPlus | COMPLEX | - |
dc.subject.keywordPlus | OXYGEN | - |
dc.subject.keywordPlus | IRON | - |
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