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dc.contributor.author남원우*
dc.contributor.author이용민*
dc.date.accessioned2023-07-31T16:31:08Z-
dc.date.available2023-07-31T16:31:08Z-
dc.date.issued2023*
dc.identifier.issn1477-9226*
dc.identifier.otherOAK-33583*
dc.identifier.urihttps://dspace.ewha.ac.kr/handle/2015.oak/265293-
dc.description.abstractNonheme nickel(ii)-mediated oxidations of hydrocarbons by meta-chloroperbenzoic acid (mCPBA) show promising activity and selectivity; however, the active species and the reaction mechanism of these reactions are still elusive after decades of efforts. Herein, a novel free radical chain mechanism of the Ni(ii)-mediated oxidation of cyclohexane by mCPBA is investigated using density functional theory calculations. In this study, we rule out the involvement of a long speculated NiII-oxyl species. Instead, an aroyloxy radical (mCBA˙) and a NiIII-hydroxyl species formed by a rate-limiting O-O homolysis of a NiII-mCPBA complex are active species in the C-H bond activation to form a carbon-centered radical R˙, where mCBA˙ is more robust than the NiIII-hydroxyl species. The nascent R˙ radical either reacts with mCPBA to form a hydroxylated product and a mCBA˙ radical to propagate the radical chain or reacts with the solvent dichloromethane to form a chlorinated product. In addition, the NiII-mCPBA complex is found for the first time to be a robust oxidant in hydroxylation of cyclohexane, with an activation energy of 13.4 kcal mol−1. These mechanistic findings support the free radical chain mechanism and enrich the mechanistic knowledge of metal-peracid oxidation systems containing transition metals after group 8 in periodic table of elements. © 2023 The Royal Society of Chemistry.*
dc.languageEnglish*
dc.publisherRoyal Society of Chemistry*
dc.titleThe elusive active species in nickel(ii)-mediated oxidations of hydrocarbons by peracids: a NiII-oxyl species, an aroyloxy radical, or a NiII-peracid complex?*
dc.typeArticle*
dc.relation.issue25*
dc.relation.volume52*
dc.relation.indexSCIE*
dc.relation.indexSCOPUS*
dc.relation.startpage8676*
dc.relation.lastpage8684*
dc.relation.journaltitleDalton Transactions*
dc.identifier.doi10.1039/d3dt01276j*
dc.identifier.wosidWOS:001003297500001*
dc.identifier.scopusid2-s2.0-85163457455*
dc.author.googleWu Z.*
dc.author.googleSun D.*
dc.author.googleLee Y.-M.*
dc.author.googleZhao Y.*
dc.author.googleNam W.*
dc.author.googleWang Y.*
dc.contributor.scopusid남원우(7006569723)*
dc.contributor.scopusid이용민(36546331100;35233855500;57192113229)*
dc.date.modifydate20240426135715*
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자연과학대학 > 화학·나노과학전공 > Journal papers
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