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 | 2016-08-28T10:08:47Z | - |
dc.date.available | 2016-08-28T10:08:47Z | - |
dc.date.issued | 2013 | * |
dc.identifier.issn | 0002-7863 | * |
dc.identifier.other | OAK-9973 | * |
dc.identifier.uri | https://dspace.ewha.ac.kr/handle/2015.oak/223626 | - |
dc.description.abstract | The reactivity of a nonheme iron(IV)-oxo complex, [(N4Py)Fe IV(O)]2+ (N4Py = N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl) methylamine), was markedly enhanced by perchloric acid (70% HClO4) in the oxidation of toluene derivatives. Toluene, which has a high one-electron oxidation potential (Eox = 2.20 V vs SCE), was oxidized by [(N4Py)FeIV(O)]2+ in the presence of HClO4 in acetonitrile (MeCN) to yield a stoichiometric amount of benzyl alcohol, in which [(N4Py)FeIV(O)]2+ was reduced to [(N4Py)Fe III(OH2)]3+. The second-order rate constant (kobs) of the oxidation of toluene derivatives by [(N4Py)Fe IV(O)]2+ increased with increasing concentration of HClO4, showing the first-order dependence on [HClO4]. A significant kinetic isotope effect (KIE) was observed when mesitylene was replaced by mesitylene-d12 in the oxidation with [(N4Py)Fe IV(O)]2+ in the absence of HClO4 in MeCN at 298 K. The KIE value drastically decreased from KIE = 31 in the absence of HClO4 to KIE = 1.0 with increasing concentration of HClO4, accompanied by the large acceleration of the oxidation rate. The absence of KIE suggests that electron transfer from a toluene derivative to the protonated iron(IV)-oxo complex ([(N4Py)FeIV(OH)]3+) is the rate-determining step in the acid-promoted oxidation reaction. The detailed kinetic analysis in light of the Marcus theory of electron transfer has revealed that the acid-promoted C-H bond cleavage proceeds via the rate-determining electron transfer from toluene derivatives to [(N4Py)FeIV(OH)] 3+ through formation of strong precursor complexes between toluene derivatives and [(N4Py)FeIV(OH)]3+. © 2013 American Chemical Society. | * |
dc.language | English | * |
dc.title | Brønsted acid-promoted C-H bond cleavage via electron transfer from toluene derivatives to a protonated nonheme iron(IV)-oxo complex with no kinetic isotope effect | * |
dc.type | Article | * |
dc.relation.issue | 13 | * |
dc.relation.volume | 135 | * |
dc.relation.index | SCI | * |
dc.relation.index | SCIE | * |
dc.relation.index | SCOPUS | * |
dc.relation.startpage | 5052 | * |
dc.relation.lastpage | 5061 | * |
dc.relation.journaltitle | Journal of the American Chemical Society | * |
dc.identifier.doi | 10.1021/ja311662w | * |
dc.identifier.wosid | WOS:000317259300034 | * |
dc.identifier.scopusid | 2-s2.0-84875790704 | * |
dc.author.google | Park J. | * |
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 | * |