Full metadata record
DC Field | Value | Language |
---|---|---|
dc.contributor.author | 남원우 | * |
dc.contributor.author | Shunichi Fukuzumi | * |
dc.contributor.author | 이용민 | * |
dc.contributor.author | 서미숙 | * |
dc.date.accessioned | 2021-12-28T16:30:06Z | - |
dc.date.available | 2021-12-28T16:30:06Z | - |
dc.date.issued | 2021 | * |
dc.identifier.issn | 0020-1669 | * |
dc.identifier.issn | 1520-510X | * |
dc.identifier.other | OAK-30607 | * |
dc.identifier.uri | https://dspace.ewha.ac.kr/handle/2015.oak/259694 | - |
dc.description.abstract | Binding of Lewis acidic metal ions and Bronsted 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)Mn-IV(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., nu(Mn-O) at similar to 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)Mn-IV(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)Mn-IV(OH)](OTf)(2) (4), with a Mn-O bond distance of 1.8043(19) angstrom 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. | * |
dc.language | English | * |
dc.publisher | AMER CHEMICAL SOC | * |
dc.title | Deeper Understanding of Mononuclear Manganese(IV)-Oxo Binding Bronsted and Lewis Acids and the Manganese(IV)-Hydroxide Complex | * |
dc.type | Article | * |
dc.relation.issue | 22 | * |
dc.relation.volume | 60 | * |
dc.relation.index | SCIE | * |
dc.relation.index | SCOPUS | * |
dc.relation.startpage | 16996 | * |
dc.relation.lastpage | 17007 | * |
dc.relation.journaltitle | INORGANIC CHEMISTRY | * |
dc.identifier.doi | 10.1021/acs.inorgchem.1c02119 | * |
dc.identifier.wosid | WOS:000720776700015 | * |
dc.identifier.scopusid | 2-s2.0-85118800586 | * |
dc.author.google | Karmalkar, Deepika G. | * |
dc.author.google | Seo, Mi Sook | * |
dc.author.google | Lee, Yong-Min | * |
dc.author.google | Kim, Youngsuk | * |
dc.author.google | Lee, Eunsung | * |
dc.author.google | Sarangi, Ritimukta | * |
dc.author.google | Fukuzumi, Shunichi | * |
dc.author.google | Nam, Wonwoo | * |
dc.contributor.scopusid | 남원우(7006569723) | * |
dc.contributor.scopusid | Shunichi Fukuzumi(35430038100;58409757400) | * |
dc.contributor.scopusid | 이용민(36546331100;35233855500;57192113229) | * |
dc.contributor.scopusid | 서미숙(7101805112) | * |
dc.date.modifydate | 20240405124941 | * |