DC Field | Value | Language |
---|---|---|
dc.contributor.author | Karmalkar, D.G. | - |
dc.contributor.author | Seo, M.S. | - |
dc.contributor.author | Lee, Y.-M. | - |
dc.contributor.author | Kim, Y. | - |
dc.contributor.author | Lee, E. | - |
dc.contributor.author | Sarangi, R. | - |
dc.contributor.author | Fukuzumi, S. | - |
dc.contributor.author | Nam, W. | - |
dc.date.accessioned | 2022-06-23T02:50:29Z | - |
dc.date.available | 2022-06-23T02:50:29Z | - |
dc.date.created | 2021-12-12 | - |
dc.date.issued | 2021-11 | - |
dc.identifier.issn | 0020-1669 | - |
dc.identifier.uri | https://oasis.postech.ac.kr/handle/2014.oak/113102 | - |
dc.description.abstract | Binding of Lewis acidic metal ions and Br��nsted acid at the metal-oxo group of high-valent metal-oxo complexes enhances their reactivities significantly in oxidation reactions. However, such a binding of Lewis acids and proton at the metal-oxo group has been questioned in several cases and remains to be clarified. Herein, we report the synthesis, characterization, and reactivity studies of a mononuclear manganese(IV)-oxo complex binding triflic acid, {[(dpaq)MnIV(O)]-HOTf}+ (1-HOTf). First, 1-HOTf was synthesized and characterized using various spectroscopic techniques, including resonance Raman (rRaman) and X-ray absorption spectroscopy/extended X-ray absorption fine structure. In particular, in rRaman experiments, we observed a linear correlation between the Mn-O stretching frequencies of 1-HOTf (e.g., ��Mn-O at ? 793 cm-1) and 1-Mn+ (Mn+ = Ca2+, Zn2+, Lu3+, Al3+, or Sc3+) and the Lewis acidities of H+ and Mn+ ions, suggesting that H+ and Mn+ bind at the metal-oxo moiety of [(dpaq)MnIV(O)]+. Interestingly, a single-crystal structure of 1-HOTf was obtained by X-ray diffraction analysis, but the structure was not an expected Mn(IV)-oxo complex but a Mn(IV)-hydroxide complex, [(dpaq)MnIV(OH)](OTf)2 (4), with a Mn-O bond distance of 1.8043(19) ? and a Mn-O stretch at 660 cm-1. More interestingly, 4 reverted to 1-HOTf upon dissolution, demonstrating that 1-HOTf and 4 are interconvertible depending on the physical states, such as 1-HOTf in solution and 4 in isolated solid. The reactivity of 1-HOTf was investigated in hydrogen atom transfer (HAT) and oxygen atom transfer (OAT) reactions and then compared with those of 1-Mn+ complexes; an interesting correlation between the Mn-O stretching frequencies of 1-HOTf and 1-Mn+ and their reactivities in the OAT and HAT reactions is reported for the first time in this study. ? 2021 American Chemical Society. | - |
dc.language | English | - |
dc.publisher | American Chemical Society | - |
dc.relation.isPartOf | Inorganic Chemistry | - |
dc.title | Deeper Understanding of Mononuclear Manganese(IV)-Oxo Binding Br��nsted and Lewis Acids and the Manganese(IV)-Hydroxide Complex | - |
dc.type | Article | - |
dc.identifier.doi | 10.1021/acs.inorgchem.1c02119 | - |
dc.type.rims | ART | - |
dc.identifier.bibliographicCitation | Inorganic Chemistry, v.60, no.22, pp.16996 - 17007 | - |
dc.identifier.wosid | 000720776700015 | - |
dc.citation.endPage | 17007 | - |
dc.citation.number | 22 | - |
dc.citation.startPage | 16996 | - |
dc.citation.title | Inorganic Chemistry | - |
dc.citation.volume | 60 | - |
dc.contributor.affiliatedAuthor | Kim, Y. | - |
dc.contributor.affiliatedAuthor | Lee, E. | - |
dc.identifier.scopusid | 2-s2.0-85118800586 | - |
dc.description.journalClass | 1 | - |
dc.description.journalClass | 1 | - |
dc.description.isOpenAccess | N | - |
dc.type.docType | Article | - |
dc.subject.keywordPlus | X-RAY-ABSORPTION | - |
dc.subject.keywordPlus | COUPLED ELECTRON-TRANSFER | - |
dc.subject.keywordPlus | INACTIVE METAL-IONS | - |
dc.subject.keywordPlus | NONHEME IRON(IV)-OXO COMPLEX | - |
dc.subject.keywordPlus | OXYGEN-EVOLVING COMPLEX | - |
dc.subject.keywordPlus | HYDROGEN-ATOM TRANSFER | - |
dc.subject.keywordPlus | H BOND ACTIVATION | - |
dc.subject.keywordPlus | WATER OXIDATION | - |
dc.subject.keywordPlus | PHOTOSYSTEM-II | - |
dc.subject.keywordPlus | DIOXYGEN ACTIVATION | - |
dc.relation.journalWebOfScienceCategory | Chemistry, Inorganic & Nuclear | - |
dc.description.journalRegisteredClass | scie | - |
dc.description.journalRegisteredClass | scopus | - |
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