Full metadata record
DC Field | Value | Language |
---|---|---|
dc.contributor.author | 남원우 | * |
dc.contributor.author | Shunichi Fukuzumi | * |
dc.contributor.author | 서미숙 | * |
dc.date.accessioned | 2021-06-07T16:31:45Z | - |
dc.date.available | 2021-06-07T16:31:45Z | - |
dc.date.issued | 2021 | * |
dc.identifier.issn | 2155-5435 | * |
dc.identifier.other | OAK-29314 | * |
dc.identifier.uri | https://dspace.ewha.ac.kr/handle/2015.oak/257676 | - |
dc.description.abstract | We report the synthesis, characterization, and electron-transfer (ET) oxidation reactivity of a chromium(V)-oxo TAML cation radical complex binding Sc3+ ion, {[ Cr-V(O)(TAML(center dot+))]-Sc3+}(3+) (2-Sc). Its precursors, such as [Cr-V(O)(TAML)](-) (1) and {[Cr-V(O)(TAML)]Sc3+}(2+) (1-Sc), were also characterized spectroscopically and/or structurally. In ET and oxygen atom transfer (OAT) reactions, while 1 and 1-Sc were sluggish oxidants, 2-Sc was a highly reactive oxidant with an extremely small reorganization energy. For example, in ET oxidation reactions, nanosecond laser-induced transient absorption measurements were performed to examine the fast ET from electron donors (e.g., ferrocene derivatives) to 2-Sc, affording a small reorganization energy (lambda = 0.26 eV) of ET, which is even much smaller than the lambda values reported in the ET reduction of heme Compound I (Cpd I) models and non-heme metal-oxo complexes. Such a small reorganization energy is ascribed to the TAML ligand centered ET reduction of 2-Sc. The lambda value of 0.26 eV was also obtained in the electron self-exchange reaction between 2-Sc and 1-Sc. In OAT reactions, the rate constants of the sulfoxidation of thioanisole derivatives by 2-Sc at -40 degrees C were much greater than those reported in the oxidation of thioanisoles by heme Cpd I and non-heme metal-oxo complexes. The reactivity of 2-Sc in hydrogen atom transfer (HAT) reactions is also discussed briefly. To the best of our knowledge, this Cr(V)-oxo TAML cation radical complex binding Sc3+ ion, {[Cr-V(O)(TAML(center dot+))]-Sc3+}(3+), with an extremely small reorganization energy is one of the most powerful high-valent metal-oxo oxidants in ET and OAT reactions. | * |
dc.language | English | * |
dc.publisher | AMER CHEMICAL SOC | * |
dc.subject | electron transfer | * |
dc.subject | oxygen atom transfer | * |
dc.subject | chromium(V)-oxo complex | * |
dc.subject | redox-inactive metal ion | * |
dc.subject | reorganization energy | * |
dc.title | A Highly Reactive Chromium(V)-Oxo TAML Cation Radical Complex in Electron Transfer and Oxygen Atom Transfer Reactions | * |
dc.type | Article | * |
dc.relation.issue | 5 | * |
dc.relation.volume | 11 | * |
dc.relation.index | SCIE | * |
dc.relation.index | SCOPUS | * |
dc.relation.startpage | 2889 | * |
dc.relation.lastpage | 2901 | * |
dc.relation.journaltitle | ACS CATALYSIS | * |
dc.identifier.doi | 10.1021/acscatal.1c00079 | * |
dc.identifier.wosid | WOS:000626844200039 | * |
dc.author.google | Hong, Young Hyun | * |
dc.author.google | Jang, Yuri | * |
dc.author.google | Ezhov, Roman | * |
dc.author.google | Seo, Mi Sook | * |
dc.author.google | Lee, Yong-Min | * |
dc.author.google | Pandey, Bhawana | * |
dc.author.google | Hong, Seungwoo | * |
dc.author.google | Pushkar, Yulia | * |
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 | 서미숙(7101805112) | * |
dc.date.modifydate | 20240405124941 | * |