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dc.contributor.author남원우-
dc.contributor.authorShunichi Fukuzumi-
dc.contributor.author이용민-
dc.date.accessioned2016-08-28T12:08:32Z-
dc.date.available2016-08-28T12:08:32Z-
dc.date.issued2009-
dc.identifier.issn0947-6539-
dc.identifier.otherOAK-6076-
dc.identifier.urihttp://dspace.ewha.ac.kr/handle/2015.oak/220363-
dc.description.abstractHigh-valent manganese(IV or V)-oxo porphyrins are considered as reactive intermediates in the oxidation of organic substrates by manganese porphyrin catalysts. We have generated MnV- and MnIV-oxo porphyrins in basic aqueous solution and investigated their reactivities in C-H bond activation of hydrocarbons. We now report that MnV- and Mn IV-oxo porphyrins are capable of activating C-H bonds of alkylaromatics, with the reactivity order of MnV-oxo>Mn IV-oxo; the reactivity of a MnV-oxo complex is 150 times greater than that of a MnIV-oxo complex in the oxidation of xanthene. The C-H bond activation of alkylaromatics by the MnV- and Mn IV-oxo porphyrins is proposed to occur through a hydrogen-atom abstraction, based on the observations of a good linear correlation between the reaction rates and the C-H bond dissociation energy (BDE) of substrates and high kinetic isotope effect (KIE) values in the oxidation of xanthene and dihydroanthracene (DHA). We have demonstrated that the disproportionation of MnIV-oxo porphyrins to MnV-oxo and MnIII porphyrins is not a feasible pathway in basic aqueous solution and that Mn IV-oxo porphyrins are able to abstract hydrogen atoms from alkylaromatics. The C-H bond activation of alkylaromatics by MnV- and MnIV-oxo species proceeds through a one-electron process, in which a MnIV-oxo porphyrin is formed as a product in the C-H bond activation by a MnV-oxo porphyrin, followed by a further reaction of the MnIV-oxo porphyrin with substrates that results in the formation of a MnIII porphyrin complex. This result is in contrast to the oxidation of sulfides by the MnV-oxo porphyrin, in which the oxidation of thioanisole by the MnV-oxo complex produces the starting Mn III porphyrin and thioanisole oxide. This result indicates that the oxidation of sulfides by the MnV-oxo species occurs by means of a two-electron oxidation process. In contrast, a MnIV-oxo porphyrin complex is not capable of oxidizing sulfides due to a low oxidizing power in basic aqueous solution. © 2009 Wiley-VCH Verlag GmbH & Co. KGaA.-
dc.languageEnglish-
dc.titleHydrogen-atom abstraction reactions by manganese(V)- and manganese(IV)-oxo porphyrin complexes in aqueous solution-
dc.typeArticle-
dc.relation.issue43-
dc.relation.volume15-
dc.relation.indexSCI-
dc.relation.indexSCIE-
dc.relation.indexSCOPUS-
dc.relation.startpage11482-
dc.relation.lastpage11489-
dc.relation.journaltitleChemistry - A European Journal-
dc.identifier.doi10.1002/chem.200901362-
dc.identifier.wosidWOS:000271992100011-
dc.identifier.scopusid2-s2.0-70350504341-
dc.author.googleArunkumar C.-
dc.author.googleLee Y.-M.-
dc.author.googleLee J.Y.-
dc.author.googleFukuzumi S.-
dc.author.googleNam W.-
dc.contributor.scopusid남원우(7006569723)-
dc.contributor.scopusidShunichi Fukuzumi(35430038100)-
dc.contributor.scopusid이용민(36546331100;35233855500)-
dc.date.modifydate20210301081004-
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