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 | 2016-08-28T12:08:28Z | - |
dc.date.available | 2016-08-28T12:08:28Z | - |
dc.date.issued | 2011 | * |
dc.identifier.issn | 0020-1669 | * |
dc.identifier.other | OAK-8125 | * |
dc.identifier.uri | https://dspace.ewha.ac.kr/handle/2015.oak/222077 | - |
dc.description.abstract | Oxidative dimerization of N,N-dimethylaniline (DMA) occurs with a nonheme iron(IV)-oxo complex, [FeIV(O)(N4Py)]2+ (N4Py = N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine), to yield the corresponding dimer, tetramethylbenzidine (TMB), in acetonitrile. The rate of the oxidative dimerization of DMA by [FeIV(O)(N4Py)]2+ is markedly enhanced by the presence of scandium triflate, Sc(OTf)3 (OTf = CF3SO3 -), when TMB is further oxidized to the radical cation (TMB•+). In contrast, we have observed the oxidative N-demethylation with para-substituted DMA substrates, since the position of the C-C bond formation to yield the dimer is blocked. The rate of the oxidative N-demethylation of para-substituted DMA by [FeIV(O) (N4Py)]2+ is also markedly enhanced by the presence of Sc(OTf) 3. In the case of para-substituted DMA derivatives with electron-donating substituents, radical cations of DMA derivatives are initially formed by Sc3+ ion-coupled electron transfer from DMA derivatives to [FeIV(O)(N4Py)]2+, giving demethylated products. Binding of Sc3+ to [FeIV(O)(N4Py)]2+ enhances the Sc3+ ion-coupled electron transfer from DMA derivatives to [Fe IV(O)(N4Py)]2+, whereas binding of Sc3+ to DMA derivatives retards the electron-transfer reaction. The complicated kinetics of the Sc3+ ion-coupled electron transfer from DMA derivatives to [FeIV(O)(N4Py)]2+ are analyzed by competition between binding of Sc3+ to DMA derivatives and to [FeIV(O)(N4Py)] 2+. The binding constants of Sc3+ to DMA derivatives increase with the increase of the electron-donating ability of the para-substituent. The rate constants of Sc3+ ion-coupled electron transfer from DMA derivatives to [FeIV(O)(N4Py)]2+, which are estimated from the binding constants of Sc3+ to DMA derivatives, agree well with those predicted from the driving force dependence of the rate constants of Sc3+ ion-coupled electron transfer from one-electron reductants to [FeIV(O)(N4Py)]2+. Thus, oxidative dimerization of DMA and N-demethylation of para-substituted DMA derivatives proceed via Sc3+ ion-coupled electron transfer from DMA derivatives to [FeIV(O)(N4Py)]2+. © 2011 American Chemical Society. | * |
dc.language | English | * |
dc.title | Scandium ion-enhanced oxidative dimerization and N -demethylation of N, N -dimethylanilines by a non-heme iron(IV)-oxo complex | * |
dc.type | Article | * |
dc.relation.issue | 22 | * |
dc.relation.volume | 50 | * |
dc.relation.index | SCI | * |
dc.relation.index | SCIE | * |
dc.relation.index | SCOPUS | * |
dc.relation.startpage | 11612 | * |
dc.relation.lastpage | 11622 | * |
dc.relation.journaltitle | Inorganic Chemistry | * |
dc.identifier.doi | 10.1021/ic201545a | * |
dc.identifier.wosid | WOS:000296830400043 | * |
dc.identifier.scopusid | 2-s2.0-81255150044 | * |
dc.author.google | Park J. | * |
dc.author.google | Morimoto Y. | * |
dc.author.google | Lee Y.-M. | * |
dc.author.google | You Y. | * |
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 | * |