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DC Field | Value | Language |
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dc.citation.endPage | 9429 | - |
dc.citation.number | 27 | - |
dc.citation.startPage | 9420 | - |
dc.citation.title | JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | - |
dc.citation.volume | 132 | - |
dc.contributor.author | Tennyson, Andrew G. | - |
dc.contributor.author | Lynch, Vincent M. | - |
dc.contributor.author | Bielawski, Christopher W. | - |
dc.date.accessioned | 2023-12-22T07:06:41Z | - |
dc.date.available | 2023-12-22T07:06:41Z | - |
dc.date.created | 2020-07-13 | - |
dc.date.issued | 2010-07 | - |
dc.description.abstract | Optimized syntheses for 1,3-dimesitylnaphthoquinimidazolium chloride [1H][Cl] and the corresponding silver NHC complex [AgCl(1)] (2) were developed, enabling access to this versatile reagent in near-quantitative yield. Transmetalation from 2 to [NiCl2(PPh3)(2)], trans-[PdCl2(PhCN)(2)], or trans-[PtCl2(PhCN)(2)] afforded the Group 10 complexes trans-[MCl2(1)(2)] (3a-c, M = Ni, Pd, and Pt, respectively) in excellent overall yield (>95%) after three steps from commercially available starting materials. Electrochemical measurements indicated that the E-1/2 and Delta E-1/2 values for the quinone reduction couples were independent of the identity of the bridging transition metal in these complexes. Whereas attempts to isolate the reduced complexes were unsuccessful, UV/vis spectroelectrochemical analysis confirmed that electrochemical reduction of 3a-c in situ afforded optical difference spectra consistent with the formation of the expected reduced species. Complex 3a was found to catalyze the Kumada cross-coupling reaction between PhMgCl and a range of bromoarenes at room temperature. Addition of 2 equiv of cobaltocene (with respect to 3a) to the coupling reaction with bromotoluene caused a decrease in catalytic activity (from 4.7 x 10(-5) to 2.7 x 10(-6) s(-1)), which was attributed to the conversion of 3a to an arrested state. Subsequent introduction of ferrocenium tetrafluoroborate (2 equiv with respect to 3a) restored a significant degree of catalytic activity (k(obs) = 1.2 x 10(-5) s(-1)). Redox-switching experiments performed over different time scales revealed that the catalyst was stable in the reduced/inactive state and that extended durations in this state did not impede catalytic reactivation upon subsequent oxidation. | - |
dc.identifier.bibliographicCitation | JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, v.132, no.27, pp.9420 - 9429 | - |
dc.identifier.doi | 10.1021/ja102686u | - |
dc.identifier.issn | 0002-7863 | - |
dc.identifier.scopusid | 2-s2.0-84908659807 | - |
dc.identifier.uri | https://scholarworks.unist.ac.kr/handle/201301/33236 | - |
dc.identifier.url | https://pubs.acs.org/doi/10.1021/ja102686u | - |
dc.identifier.wosid | 000279745700042 | - |
dc.language | 영어 | - |
dc.publisher | AMER CHEMICAL SOC | - |
dc.title | Arrested Catalysis: Controlling Kumada Coupling Activity via a Redox-Active N-Heterocyclic Carbene | - |
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 | TRANSITION-METAL-COMPLEXES | - |
dc.subject.keywordPlus | C BOND FORMATION | - |
dc.subject.keywordPlus | EFFICIENT CATALYSTS | - |
dc.subject.keywordPlus | PALLADIUM COMPLEXES | - |
dc.subject.keywordPlus | CARBONYL-COMPOUNDS | - |
dc.subject.keywordPlus | OLEFIN METATHESIS | - |
dc.subject.keywordPlus | GRIGNARD-REAGENTS | - |
dc.subject.keywordPlus | ELECTRON-TRANSFER | - |
dc.subject.keywordPlus | REVERSIBLY ALTER | - |
dc.subject.keywordPlus | TANDEM CATALYSIS | - |
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