Full metadata record
DC Field | Value | Language |
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dc.contributor.author | 남원우 | * |
dc.contributor.author | Shunichi Fukuzumi | * |
dc.contributor.author | 이용민 | * |
dc.date.accessioned | 2016-08-28T10:08:45Z | - |
dc.date.available | 2016-08-28T10:08:45Z | - |
dc.date.issued | 2012 | * |
dc.identifier.issn | 0020-1669 | * |
dc.identifier.other | OAK-9212 | * |
dc.identifier.uri | https://dspace.ewha.ac.kr/handle/2015.oak/223005 | - |
dc.description.abstract | The rate of oxidation of 2,5-dimethoxybenzyl alcohol (2,5-(MeO) 2C6H3CH2OH) by [Fe IV(O)(N4Py)]2+ (N4Py = N,N-bis(2-pyridylmethyl)-N-bis(2- pyridyl)methylamine) was enhanced significantly in the presence of Sc(OTf) 3 (OTf- = trifluoromethanesulfonate) in acetonitrile (e.g., 120-fold acceleration in the presence of Sc3+). Such a remarkable enhancement of the reactivity of [FeIV(O)(N4Py)] 2+ in the presence of Sc3+ was accompanied by the disappearance of a kinetic deuterium isotope effect. The radical cation of 2,5-(MeO)2C6H3CH2OH was detected in the course of the reaction in the presence of Sc3+. The dimerized alcohol and aldehyde were also produced in addition to the monomer aldehyde in the presence of Sc3+. These results indicate that the reaction mechanism is changed from one-step hydrogen atom transfer (HAT) from 2,5-(MeO)2C6H3CH2OH to [Fe IV(O)(N4Py)]2+ in the absence of Sc3+ to stepwise Sc3+-coupled electron transfer, followed by proton transfer in the presence of Sc3+. In contrast, neither acceleration of the rate nor the disappearance of the kinetic deuterium isotope effect was observed in the oxidation of benzyl alcohol (C6H5CH2OH) by [FeIV(O)(N4Py)]2+ in the presence of Sc(OTf) 3. Moreover, the rate constants determined in the oxidation of various benzyl alcohol derivatives by [FeIV(O)(N4Py)]2+ in the presence of Sc(OTf)3 (10 mM) were compared with those of Sc 3+-coupled electron transfer from one-electron reductants to [Fe IV(O)(N4Py)]2+ at the same driving force of electron transfer. This comparison revealed that the borderline of the change in the mechanism from HAT to stepwise Sc3+-coupled electron transfer and proton transfer is dependent on the one-electron oxidation potential of benzyl alcohol derivatives (ca. 1.7 V vs SCE). © 2012 American Chemical Society. | * |
dc.language | English | * |
dc.title | Mechanistic borderline of one-step hydrogen atom transfer versus stepwise Sc3+-coupled electron transfer from benzyl alcohol derivatives to a non-heme iron(IV)-oxo complex | * |
dc.type | Article | * |
dc.relation.issue | 18 | * |
dc.relation.volume | 51 | * |
dc.relation.index | SCI | * |
dc.relation.index | SCIE | * |
dc.relation.index | SCOPUS | * |
dc.relation.startpage | 10025 | * |
dc.relation.lastpage | 10036 | * |
dc.relation.journaltitle | Inorganic Chemistry | * |
dc.identifier.doi | 10.1021/ic3016723 | * |
dc.identifier.wosid | WOS:000308778000051 | * |
dc.identifier.scopusid | 2-s2.0-84866429123 | * |
dc.author.google | Morimoto Y. | * |
dc.author.google | Park J. | * |
dc.author.google | Suenobu T. | * |
dc.author.google | Lee Y.-M. | * |
dc.author.google | Nam W. | * |
dc.author.google | Fukuzumi S. | * |
dc.contributor.scopusid | 남원우(7006569723) | * |
dc.contributor.scopusid | Shunichi Fukuzumi(35430038100;58409757400) | * |
dc.contributor.scopusid | 이용민(36546331100;35233855500;57192113229) | * |
dc.date.modifydate | 20240401081001 | * |