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DC Field | Value | Language |
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dc.citation.endPage | 3299 | - |
dc.citation.number | 8 | - |
dc.citation.startPage | 3286 | - |
dc.citation.title | JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | - |
dc.citation.volume | 135 | - |
dc.contributor.author | Liu, Lei V. | - |
dc.contributor.author | Hong, Seungwoo | - |
dc.contributor.author | Cho, Jaeheung | - |
dc.contributor.author | Nam, Wonwoo | - |
dc.contributor.author | Solomon, Edward I. | - |
dc.date.accessioned | 2023-12-22T04:11:27Z | - |
dc.date.available | 2023-12-22T04:11:27Z | - |
dc.date.created | 2020-09-03 | - |
dc.date.issued | 2013-02 | - |
dc.description.abstract | The geometric and electronic structures and reactivity of an S = 5/2 (HS) mononuclear nonheme (TMC)Fe-III-OOH complex are studied by spectroscopies, calculations, and kinetics and compared with the results of previous studies of S = 1/2 (LS) Fe-III-OOH complexes to understand parallels and differences in mechanisms of O-O bond homolysis and electrophilic H-atom abstraction reactions. The homolysis reaction of the HS [(TMC)Fe-III-OOH](2+) complex is found to involve axial ligand coordination and a crossing to the LS surface for O-O bond homolysis. Both HS and LS Fe-III-OOH complexes are found to perform direct H-atom abstraction reactions but with very different reaction coordinates. For the LS Fe-III-OOH, the transition state is late in O-O and early in C-H coordinates. However, for the HS Fe-III-OOH, the transition state is early in O-O and further along in the C-H coordinate. In addition, there is a significant amount of electron transfer from the substrate to the HS Fe-III-OOH at transition state, but that does not occur in the LS transition state. Thus, in contrast to the behavior of LS Fe-III-OOH, the H-atom abstraction reactivity of HS Fe-III-OOH is found to be highly dependent on both the ionization potential and the C-H bond strength of the substrate. LS Fe-III-OOH is found to be more effective in H-atom abstraction for strong C-H bonds, while the higher reduction potential of HS Fe-III-OOH allows it to be active in electrophilic reactions without the requirement of O-O bond cleavage. This is relevant to the Rieske dioxygenases, which are proposed to use a HS Fe-III-OOH to catalyze cis-dihydroxylation of a wide range of aromatic compounds. | - |
dc.identifier.bibliographicCitation | JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, v.135, no.8, pp.3286 - 3299 | - |
dc.identifier.doi | 10.1021/ja400183g | - |
dc.identifier.issn | 0002-7863 | - |
dc.identifier.scopusid | 2-s2.0-84874631578 | - |
dc.identifier.uri | https://scholarworks.unist.ac.kr/handle/201301/48127 | - |
dc.identifier.url | https://pubs.acs.org/doi/10.1021/ja400183g | - |
dc.identifier.wosid | 000315618900064 | - |
dc.language | 영어 | - |
dc.publisher | AMER CHEMICAL SOC | - |
dc.title | Comparison of High-Spin and Low-Spin Nonheme Fe-III-OOH Complexes in O-O Bond Homolysis and H-Atom Abstraction Reactivities | - |
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 | ELECTRONIC-STRUCTURE | - |
dc.subject.keywordPlus | ACTIVATED BLEOMYCIN | - |
dc.subject.keywordPlus | HYDROGEN-PEROXIDE | - |
dc.subject.keywordPlus | CIS-DIHYDROXYLATION | - |
dc.subject.keywordPlus | MECHANISM | - |
dc.subject.keywordPlus | MODELS | - |
dc.subject.keywordPlus | DNA | - |
dc.subject.keywordPlus | CHEMISTRY | - |
dc.subject.keywordPlus | OXIDATION | - |
dc.subject.keywordPlus | CLEAVAGE | - |
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