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DC Field | Value | Language |
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dc.citation.endPage | 15805 | - |
dc.citation.number | 23 | - |
dc.citation.startPage | 15796 | - |
dc.citation.title | JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | - |
dc.citation.volume | 146 | - |
dc.contributor.author | Lee, Yuri | - |
dc.contributor.author | Moon, Dohyun | - |
dc.contributor.author | Cho, Jaeheung | - |
dc.date.accessioned | 2024-06-20T10:05:11Z | - |
dc.date.available | 2024-06-20T10:05:11Z | - |
dc.date.created | 2024-06-17 | - |
dc.date.issued | 2024-06 | - |
dc.description.abstract | A series of mononuclear manganese(III)-hydroxo and -aqua complexes, [Mn-III(TBDAP)(OH)(2)](+) (1), [Mn-III(TBDAP)(OH)(OH2)](2+) (2) and [Mn-III(TBDAP)(OH2)(2)](3+) (3), were prepared from a manganese(II) precursor and confirmed using various methods including X-ray crystallography. Thermodynamic analysis showed that protonation from hydroxo to aqua species resulted in increased redox potentials (E-1/2) in the order of 1 (-0.15 V) < 2 (0.56 V) < 3 (1.11 V), while pK(a) values exhibited a reverse trend in the order of 3 (3.87) < 2 (11.84). Employing the Bordwell Equation, the O-H bond dissociation free energies (BDFE) of [Mn-II(TBDAP)(OH)(OH2)](+) and [Mn-II(TBDAP)(OH2)(2)](2+), related to the driving force of 1 and 2 in hydrogen atom transfer (HAT), were determined as 75.3 and 77.3 kcal mol(-1), respectively. It was found that the thermodynamic driving force of 2 in HAT becomes greater than that of 1 as the redox potential of 2 increases through protonation from 1 to 2. Kinetic studies on electrophilic reactions using a variety of substrates revealed that 1 is only weakly reactive with O-H bonds, whereas 2 can activate aliphatic C-H bonds in addition to O-H bonds. The reaction rates increased by 1.4 x 10(4)-fold for the O-H bonds by 2 over 1, which was explained by the difference in BDFE and the tunneling effect. Furthermore, 3, possessing the highest redox potential value, was found to undergo an aromatic C-H bond activation reaction under mild conditions. These results provide valuable insights into enhancing electrophilic reactivity by modulating the redox potential of manganese(III)-hydroxo and -aqua complexes through protonation. | - |
dc.identifier.bibliographicCitation | JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, v.146, no.23, pp.15796 - 15805 | - |
dc.identifier.doi | 10.1021/jacs.4c01927 | - |
dc.identifier.issn | 0002-7863 | - |
dc.identifier.scopusid | 2-s2.0-85195325645 | - |
dc.identifier.uri | https://scholarworks.unist.ac.kr/handle/201301/83002 | - |
dc.identifier.wosid | 001238280300001 | - |
dc.language | 영어 | - |
dc.publisher | AMER CHEMICAL SOC | - |
dc.title | Controlling Redox Potential of a Manganese(III)-Bis(hydroxo) Complex through Protonation and the Hydrogen-Atom Transfer Reactivity | - |
dc.type | Article | - |
dc.description.isOpenAccess | FALSE | - |
dc.relation.journalWebOfScienceCategory | Chemistry, Multidisciplinary | - |
dc.relation.journalResearchArea | Chemistry | - |
dc.type.docType | Article; Early Access | - |
dc.description.journalRegisteredClass | scie | - |
dc.description.journalRegisteredClass | scopus | - |
dc.subject.keywordPlus | PHOTOSYSTEM-II | - |
dc.subject.keywordPlus | MONONUCLEAR | - |
dc.subject.keywordPlus | ACTIVATION | - |
dc.subject.keywordPlus | CHEMISTRY | - |
dc.subject.keywordPlus | CRYSTAL-STRUCTURE | - |
dc.subject.keywordPlus | MANGANESE-LIPOXYGENASE | - |
dc.subject.keywordPlus | OXIDATION | - |
dc.subject.keywordPlus | KINETICS | - |
dc.subject.keywordPlus | ACIDS | - |
dc.subject.keywordPlus | ELECTRON-TRANSFER REACTIVITY | - |
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