Full metadata record
DC Field | Value | Language |
---|---|---|
dc.contributor.author | 남원우 | * |
dc.contributor.author | 이용민 | * |
dc.date.accessioned | 2023-07-31T16:31:08Z | - |
dc.date.available | 2023-07-31T16:31:08Z | - |
dc.date.issued | 2023 | * |
dc.identifier.issn | 1477-9226 | * |
dc.identifier.other | OAK-33583 | * |
dc.identifier.uri | https://dspace.ewha.ac.kr/handle/2015.oak/265293 | - |
dc.description.abstract | Nonheme 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.language | English | * |
dc.publisher | Royal Society of Chemistry | * |
dc.title | The 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.type | Article | * |
dc.relation.issue | 25 | * |
dc.relation.volume | 52 | * |
dc.relation.index | SCIE | * |
dc.relation.index | SCOPUS | * |
dc.relation.startpage | 8676 | * |
dc.relation.lastpage | 8684 | * |
dc.relation.journaltitle | Dalton Transactions | * |
dc.identifier.doi | 10.1039/d3dt01276j | * |
dc.identifier.wosid | WOS:001003297500001 | * |
dc.identifier.scopusid | 2-s2.0-85163457455 | * |
dc.author.google | Wu Z. | * |
dc.author.google | Sun D. | * |
dc.author.google | Lee Y.-M. | * |
dc.author.google | Zhao Y. | * |
dc.author.google | Nam W. | * |
dc.author.google | Wang Y. | * |
dc.contributor.scopusid | 남원우(7006569723) | * |
dc.contributor.scopusid | 이용민(36546331100;35233855500;57192113229) | * |
dc.date.modifydate | 20240426135715 | * |