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DC Field | Value | Language |
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dc.citation.endPage | 1508 | - |
dc.citation.number | 4 | - |
dc.citation.startPage | 1502 | - |
dc.citation.title | CHEMICAL SCIENCE | - |
dc.citation.volume | 4 | - |
dc.contributor.author | Cho, Jaeheung | - |
dc.contributor.author | Kang, Hye Yeon | - |
dc.contributor.author | Liu, Lei V. | - |
dc.contributor.author | Sarangi, Ritimukta | - |
dc.contributor.author | Solomon, Edward I. | - |
dc.contributor.author | Nam, Wonwoo | - |
dc.date.accessioned | 2023-12-22T04:09:14Z | - |
dc.date.available | 2023-12-22T04:09:14Z | - |
dc.date.created | 2020-09-03 | - |
dc.date.issued | 2013-03 | - |
dc.description.abstract | Mononuclear metal-dioxygen adducts, such as metal-superoxo and -peroxo species, are generated as key intermediates in the catalytic cycles of dioxygen activation by heme and non-heme metalloenzymes. We have shown recently that the geometric and electronic structure of the Ni–O2 core in [Ni(n-TMC)(O2)]+ (n = 12 and 14) varies depending on the ring size of the supporting TMC ligand. In this study, mononuclear Ni(II)-superoxo and Ni(III)-peroxo complexes bearing a common macrocylic 13-TMC ligand, such as [NiII(13-TMC)(O2)]+ and [NiIII(13-TMC)(O2)]+, were synthesized in the reaction of [NiII(13-TMC)(CH3CN)]2+ and H2O2 in the presence of tetramethylammonium hydroxide (TMAH) and triethylamine (TEA), respectively. The Ni(II)-superoxo and Ni(III)-peroxo complexes bearing the common 13-TMC ligand were successfully characterized by various spectroscopic methods, X-ray crystallography and DFT calculations. Based on the combined experimental and theoretical studies, we conclude that the superoxo ligand in [NiII(13-TMC)(O2)]+ is bound in an end-on fashion to the nickel(II) center, whereas the peroxo ligand in [NiIII(13-TMC)(O2)]+ is bound in a side-on fashion to the nickel(III) center. Reactivity studies performed with the Ni(II)-superoxo and Ni(III)-peroxo complexes toward organic substrates reveal that the former possesses an electrophilic character, whereas the latter is an active oxidant in nucleophilic reaction. | - |
dc.identifier.bibliographicCitation | CHEMICAL SCIENCE, v.4, no.4, pp.1502 - 1508 | - |
dc.identifier.doi | 10.1039/c3sc22173c | - |
dc.identifier.issn | 2041-6520 | - |
dc.identifier.scopusid | 2-s2.0-84874611770 | - |
dc.identifier.uri | https://scholarworks.unist.ac.kr/handle/201301/48129 | - |
dc.identifier.url | https://pubs.rsc.org/en/content/articlelanding/2013/SC/c3sc22173c#!divAbstract | - |
dc.identifier.wosid | 000315597900013 | - |
dc.language | 영어 | - |
dc.publisher | ROYAL SOC CHEMISTRY | - |
dc.title | Mononuclear nickel(II)-superoxo and nickel(III)-peroxo complexes bearing a common macrocyclic TMC ligand | - |
dc.type | Article | - |
dc.description.isOpenAccess | FALSE | - |
dc.relation.journalWebOfScienceCategory | Chemistry, Multidisciplinary | - |
dc.relation.journalResearchArea | Chemistry | - |
dc.type.docType | Article | - |
dc.description.journalRegisteredClass | scie | - |
dc.description.journalRegisteredClass | scopus | - |
dc.subject.keywordPlus | C-H ACTIVATION | - |
dc.subject.keywordPlus | DIOXYGEN ACTIVATION | - |
dc.subject.keywordPlus | SPECTROSCOPIC CHARACTERIZATION | - |
dc.subject.keywordPlus | ELECTRONIC-STRUCTURE | - |
dc.subject.keywordPlus | REACTIVITY | - |
dc.subject.keywordPlus | SUPEROXO | - |
dc.subject.keywordPlus | ENZYMES | - |
dc.subject.keywordPlus | SITES | - |
dc.subject.keywordPlus | BOND | - |
dc.subject.keywordPlus | O-2 | - |
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