Full metadata record
DC Field | Value | Language |
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dc.contributor.author | Noh, Hyeonju | - |
dc.contributor.author | Jeong, Donghyun | - |
dc.contributor.author | Ohta, Takehiro | - |
dc.contributor.author | Ogura, Takashi | - |
dc.contributor.author | Valentine, Joan Selverstone | - |
dc.contributor.author | Cho, Jaeheung | - |
dc.date.available | 2017-09-11T03:33:50Z | - |
dc.date.created | 2017-09-11 | - |
dc.date.issued | 2017-08 | - |
dc.identifier.issn | 0002-7863 | - |
dc.identifier.uri | http://hdl.handle.net/20.500.11750/4413 | - |
dc.description.abstract | A mononuclear side-on peroxocobalt(III) complex with a tetradentate macrocyclic ligand, [CoIII(TBDAP)(O2)]+ (1), shows a novel and facile mode of dioxygenase-like reactivity with nitriles (R - C=N; R = Me, Et, and Ph) to produce the corresponding mononuclear hydroximatocobalt(III) complexes, [CoIII(TBDAP)(R - C(=NO)O)]+, in which the nitrile moiety is oxidized by two oxygen atoms of the peroxo group. The overall reaction proceeds in one-pot under ambient conditions (ca. 1 h, 40 °C). 18O-Labeling experiments confirm that both oxygen atoms are derived from the peroxo ligand. The structures of all products, hydroximatocobalt(III) complexes, were confirmed by X-ray crystallography and various spectroscopic techniques. Kinetic studies including the Hammett analysis and isotope labeling experiments suggest that the mechanistic mode of 1 for activation of nitriles occurs via a concerted mechanism. This novel reaction would be significantly valuable for expanding the chemistry for nitrile activation and utilization. © 2017 American Chemical Society. | - |
dc.language | English | - |
dc.publisher | American Chemical Society | - |
dc.title | Distinct Reactivity of a Mononuclear Peroxocobalt(III) Species toward Activation of Nitriles | - |
dc.type | Article | - |
dc.identifier.doi | 10.1021/jacs.7b04479 | - |
dc.identifier.scopusid | 2-s2.0-85027419532 | - |
dc.identifier.bibliographicCitation | Journal of the American Chemical Society, v.139, no.32, pp.10960 - 10963 | - |
dc.description.isOpenAccess | FALSE | - |
dc.subject.keywordPlus | COMPLEXES | - |
dc.subject.keywordPlus | HYDRATASE | - |
dc.subject.keywordPlus | HYDROLASES | - |
dc.subject.keywordPlus | LIGANDS | - |
dc.subject.keywordPlus | IRON | - |
dc.citation.endPage | 10963 | - |
dc.citation.number | 32 | - |
dc.citation.startPage | 10960 | - |
dc.citation.title | Journal of the American Chemical Society | - |
dc.citation.volume | 139 | - |
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