Full metadata record
DC Field | Value | Language |
---|---|---|
dc.contributor.author | 남원우 | * |
dc.date.accessioned | 2022-03-29T16:31:04Z | - |
dc.date.available | 2022-03-29T16:31:04Z | - |
dc.date.issued | 2022 | * |
dc.identifier.issn | 1477-9226 | * |
dc.identifier.other | OAK-31110 | * |
dc.identifier.uri | https://dspace.ewha.ac.kr/handle/2015.oak/260950 | - |
dc.description.abstract | High-valence metal-oxo (M-O, M = Fe, Mn, etc.) species are well-known reaction intermediates that are responsible for a wide range of pivotal oxygenation reactions and water oxidation reactions in metalloenzymes. Although extensive efforts have been devoted to synthesizing and identifying such complexes in biomimetic studies, the structure-function relationship and related reaction mechanisms of these reaction intermediates remain elusive, especially for the cobalt-oxygen species. In the present manuscript, the calculated results demonstrate that the tetraamido macrocycle ligated cobalt complex, Co(O)(TAML) (1), behaves like a chameleon: the electronic structure varies from a cobalt(iii)-oxyl species to a cobalt(iv)-oxo species when a Lewis acid Sc3+ salt coordinates or an acidic hydrocarbon attacks 1. The dichotomous correlation between the reaction rates of C-H bond activation by 1 and the bond dissociation energy (BDE) vs. the acidity (pKa) was rationalized for the first time by different reaction mechanisms: for normal C-H bond activation, the Co(iii)-oxyl species directly activates the C-H bond via a hydrogen atom transfer (HAT) mechanism, whereas for acidic C-H bond activation, the Co(iii)-oxyl species evolves to a Co(iv)-oxo species to increase the basicity of the oxygen to activate the acidic C-H bond, via a novel PCET(PT) mechanism (proton-coupled electron transfer with a PT(proton-transfer)-like transition state). These theoretical findings will enrich the knowledge of biomimetic metal-oxygen chemistry. © The Royal Society of Chemistry | * |
dc.language | English | * |
dc.publisher | Royal Society of Chemistry | * |
dc.title | The chameleon-like nature of elusive cobalt-oxygen intermediates in C-H bond activation reactions | * |
dc.type | Article | * |
dc.relation.issue | 11 | * |
dc.relation.volume | 51 | * |
dc.relation.index | SCIE | * |
dc.relation.index | SCOPUS | * |
dc.relation.startpage | 4317 | * |
dc.relation.lastpage | 4323 | * |
dc.relation.journaltitle | Dalton Transactions | * |
dc.identifier.doi | 10.1039/d2dt00224h | * |
dc.identifier.wosid | WOS:000760907000001 | * |
dc.identifier.scopusid | 2-s2.0-85126830486 | * |
dc.author.google | Zhou A. | * |
dc.author.google | Cao X. | * |
dc.author.google | Chen H. | * |
dc.author.google | Sun D. | * |
dc.author.google | Zhao Y. | * |
dc.author.google | Nam W. | * |
dc.author.google | Wang Y. | * |
dc.contributor.scopusid | 남원우(7006569723) | * |
dc.date.modifydate | 20240116111857 | * |