Full metadata record
DC Field | Value | Language |
---|---|---|
dc.contributor.author | 남원우 | * |
dc.contributor.author | Shunichi Fukuzumi | * |
dc.contributor.author | 이용민 | * |
dc.date.accessioned | 2019-02-26T16:30:02Z | - |
dc.date.available | 2019-02-26T16:30:02Z | - |
dc.date.issued | 2019 | * |
dc.identifier.issn | 0002-7863 | * |
dc.identifier.other | OAK-24428 | * |
dc.identifier.uri | https://dspace.ewha.ac.kr/handle/2015.oak/249374 | - |
dc.description.abstract | Outer-sphere electron transfer from styrene, thioanisole, and toluene derivatives to a triflic acid (HOTf)-bound nonheme Mn(IV)-oxo complex, [(N4Py)-mn Mn-IV(O)](2+)-(HOTf)(2) (N4Py = N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine), has been shown to be the rate determining step of different types of redox reactions such as epoxidation, sulfoxidation, and hydroxylation of styrene, thioanisole, and toluene derivatives, respectively, by [(N4Py)-Mn-IV(O)](2+)-(HOTf)(2). The rate constants of HOTf-promoted epoxidation of all styrene derivatives with [(N4Py)-Mn-IV(O)](2+) and electron transfer from electron donors to [(N4Py)Mn-V(O)](2+) exhibit a remarkably unified correlation with the driving force of outer-sphere electron transfer in light of the Marcus theory of electron transfer. The same electron transfer driving force dependence is observed in the oxygen atom transfer from [(N4Py)Mn-IV(O)](2+)-(HOTf)(2) to thioanisole derivatives as well as in the hydrogen atom transfer from toluene derivatives to [(N4Py)Mn-IV(O)](2+)-(HOTf)2. Thus, mechanisms of oxygen atom transfer (epoxidation and sulfoxidation) reactions of styrene and thioanisole derivatives and hydrogen atom transfer (hydroxylation) reactions of toluene derivatives by [(N4Py)Mn-IV(O)](2+)-(HOTf)(2) have been unified for the first time as the same reaction pathway via outer-sphere electron transfer, followed by the fast bond-forming step, which exhibits the singly unified electron-transfer driving force dependence of the rate constants as outer-sphere electron-transfer reactions. In the case of the epoxidation of cis-stilbene by [(N4Py)Mn-IV(O)](2+)-(HOTf)(2), the isomerization of cis-stilbene radical cation to trans-stilbene radical cation occurs after outer-sphere electron transfer from cis-stilbene to [(N4Py)Mn-IV(O)](2+)-(HOTf)(2) to yield trans-stilbene oxide selectively, which is also taken as evidence for the occurrence of electron transfer in the acid-catalyzed epoxidation. | * |
dc.language | English | * |
dc.publisher | AMER CHEMICAL SOC | * |
dc.title | Unified Mechanism of Oxygen Atom Transfer and Hydrogen Atom Transfer Reactions with a Triflic Acid-Bound Nonheme Manganese(IV)-Oxo Complex via Outer-Sphere Electron Transfer | * |
dc.type | Article | * |
dc.relation.issue | 6 | * |
dc.relation.volume | 141 | * |
dc.relation.index | SCIE | * |
dc.relation.index | SCOPUS | * |
dc.relation.startpage | 2614 | * |
dc.relation.lastpage | 2622 | * |
dc.relation.journaltitle | JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | * |
dc.identifier.doi | 10.1021/jacs.8b12935 | * |
dc.identifier.wosid | WOS:000459222100055 | * |
dc.identifier.scopusid | 2-s2.0-85061482025 | * |
dc.author.google | Lee, Yong-Min | * |
dc.author.google | Kim, Surin | * |
dc.author.google | Ohkubo, Kei | * |
dc.author.google | Kim, Kyung-Ha | * |
dc.author.google | Nam, Wonwoo | * |
dc.author.google | Fukuzumi, Shunichi | * |
dc.contributor.scopusid | 남원우(7006569723) | * |
dc.contributor.scopusid | Shunichi Fukuzumi(35430038100;58409757400) | * |
dc.contributor.scopusid | 이용민(36546331100;35233855500;57192113229) | * |
dc.date.modifydate | 20240426135715 | * |