Full metadata record
DC Field | Value | Language |
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dc.contributor.author | Kim, Bohee | - |
dc.contributor.author | Jeong, Donghyun | - |
dc.contributor.author | Ohta, Takehiro | - |
dc.contributor.author | Cho, Jaeheung | - |
dc.date.accessioned | 2019-08-22T02:53:31Z | - |
dc.date.available | 2019-08-22T02:53:31Z | - |
dc.date.created | 2019-08-20 | - |
dc.date.issued | 2019-07 | - |
dc.identifier.issn | 2399-3669 | - |
dc.identifier.uri | http://hdl.handle.net/20.500.11750/10446 | - |
dc.description.abstract | Copper(II)-hydroperoxo species are often detected as key intermediates in metalloenzymes and biomimetic compounds containing copper. However, the only reactivity has previously been observed for the copper(II)-hydroperoxo complexes is electrophilic, occurring through O-O bond cleavage. Here we report that a mononuclear end-on copper(II)-hydroperoxo complex, which has been successfully characterized by various physicochemical methods including UV-vis, rRaman, CSI-MS and EPR, is a reactive oxidant that utilizes a nucleophilic mechanism. In addition, DFT calculations fully support the electronic structure of this complex as a copper(II)-hydroperoxo complex with trigonal bipyramidal coordination geometry. A positive Hammett ρ value (2.0(3)) is observed in the reaction of copper(II)-hydroperoxo complex with para-substituted acyl chlorides, which clearly indicates nucleophilic character for the copper(II)-hydroperoxo complex. The copper(II)-hydroperoxo complex is an especially reactive oxidant in aldehyde deformylation with 2-PPA and CCA relative to the other metal-bound reactive oxygen species reported so far. The observation of nucleophilic reactivity for a copper(II)-hydroperoxo species expands the known chemistry of metal-reactive oxygen species. © 2019, The Author(s). | - |
dc.language | English | - |
dc.publisher | Nature Publishing Group | - |
dc.title | Nucleophilic reactivity of a copper(II)-hydroperoxo complex | - |
dc.type | Article | - |
dc.identifier.doi | 10.1038/s42004-019-0187-3 | - |
dc.identifier.scopusid | 2-s2.0-85071052317 | - |
dc.identifier.bibliographicCitation | Communications Chemistry, v.2, no.1, pp.81 | - |
dc.description.isOpenAccess | TRUE | - |
dc.subject.keywordPlus | HYDROGEN-BONDING INTERACTION | - |
dc.subject.keywordPlus | THERMAL-STABILITY | - |
dc.subject.keywordPlus | COPPER(I) COMPLEX | - |
dc.subject.keywordPlus | MONONUCLEAR | - |
dc.subject.keywordPlus | HYDROXYLATION | - |
dc.subject.keywordPlus | PEROXO | - |
dc.subject.keywordPlus | SPECTROSCOPY | - |
dc.subject.keywordPlus | DERIVATIVES | - |
dc.subject.keywordPlus | CHEMISTRY | - |
dc.subject.keywordPlus | LIGANDS | - |
dc.citation.number | 1 | - |
dc.citation.startPage | 81 | - |
dc.citation.title | Communications Chemistry | - |
dc.citation.volume | 2 | - |