Self-assembled M12L24 nanospheres as a reaction vessel to facilitate a dinuclear Cu(i) catalyzed cyclization reaction
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Other documents of the author: Gonell, Sergio; Caumes, Xavier; Orth, Nicole; Ivanovic-Burmazovic, Ivana; Reek, Joost
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comunitat-uji-handle2:10234/7053
comunitat-uji-handle3:10234/8639
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Title
Self-assembled M12L24 nanospheres as a reaction vessel to facilitate a dinuclear Cu(i) catalyzed cyclization reactionDate
2019Publisher
Royal Society of ChemistryISSN
2041-6520Bibliographic citation
GONELL, Sergio, et al. Self-assembled M 12 L 24 nanospheres as a reaction vessel to facilitate a dinuclear Cu (i) catalyzed cyclization reaction. Chemical science, 2019, 10.5: 1316-1321Type
info:eu-repo/semantics/articleVersion
info:eu-repo/semantics/publishedVersionAbstract
The application of large M12L24 nanospheres allows the pre-concentration of catalysts to reach high local concentrations, facilitating reactions that proceed through dinuclear mechanisms. The mechanism of the copper ... [+]
The application of large M12L24 nanospheres allows the pre-concentration of catalysts to reach high local concentrations, facilitating reactions that proceed through dinuclear mechanisms. The mechanism of the copper(I)-catalyzed cyclization of 4-pentynoic acid has been elucidated by means of a detailed mechanistic study. The kinetics of the reaction show a higher order in copper, indicating the formation of a bis-Cu intermediate as the key rate determining step of the reaction. This intermediate was further identified during catalysis by CIS-HRMS analysis of the reaction mixture. Based on the mechanistic findings, an M12L24 nanosphere was applied that can bind up to 12 copper catalysts by hydrogen bonding. This pre-organization of copper catalysts in the nanosphere results in a high local concentration of copper leading to higher reaction rates and turnover numbers as the dinuclear pathway is favored. [-]
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Chemical science, 2019, 10.5: 1316-1321Funder Name
University of Amsterdam and by the European Research Council
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ERC Advanced Grant 339786-NAT_CAT
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© The Royal Society of Chemistry 2019
info:eu-repo/semantics/openAccess
info:eu-repo/semantics/openAccess
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