Silica-Supported Cu Nanoparticle Catalysts for Alkyne Semihydrogenation: Effect of Ligands on Rates and Selectivity

Narrowly dispersed, silica-supported Cu nanoparticles (ca. 2 nm) prepared via surface organometallic chemistry from a mesityl complex [Cu5Mes5] are highly active for the hydrogenation of a broad range of alkynes. High-throughput experimentation allows for identifying the optimal ligand and reaction...

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Bibliographic Details
Published in:Journal of the American Chemical Society Vol. 138; no. 50; pp. 16502 - 16507
Main Authors: Fedorov, Alexey, Liu, Hsueh-Ju, Lo, Hung-Kun, Copéret, Christophe
Format: Journal Article
Language:English
Published: United States American Chemical Society 21-12-2016
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Summary:Narrowly dispersed, silica-supported Cu nanoparticles (ca. 2 nm) prepared via surface organometallic chemistry from a mesityl complex [Cu5Mes5] are highly active for the hydrogenation of a broad range of alkynes. High-throughput experimentation allows for identifying the optimal ligand and reaction conditions to turn these supported Cu nanoparticles into highly chemo- and stereoselective catalysts for the preparation of Z-olefins (overall, 23 examples). For instance, PCy3-modified Cu nanoparticles semihydrogenate 1-phenyl-1-propyne to cis-β-methylstyrene (20 bar H2, 40 °C) with turnover number and turnover frequency of ca. 540 and 1.9 min–1, respectively, and with 94% selectivity at full conversion.
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ISSN:0002-7863
1520-5126
DOI:10.1021/jacs.6b10817