ETH Zürich , Department of Chemistry and Applied Biosciences, Vladimir-Prelog-Weg 1-5, CH-8093 Zürich, Switzerland.
J Am Chem Soc. 2016 Dec 21;138(50):16502-16507. doi: 10.1021/jacs.6b10817. Epub 2016 Dec 7.
Narrowly dispersed, silica-supported Cu nanoparticles (ca. 2 nm) prepared via surface organometallic chemistry from a mesityl complex [CuMes] 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, PCy-modified Cu nanoparticles semihydrogenate 1-phenyl-1-propyne to cis-β-methylstyrene (20 bar H, 40 °C) with turnover number and turnover frequency of ca. 540 and 1.9 min, respectively, and with 94% selectivity at full conversion.
窄分布的、通过表面有机金属化学从均三甲苯配合物[CuMes]制备的负载在二氧化硅上的铜纳米粒子（约 2nm）对炔烃的加氢具有很高的活性。高通量实验允许确定最佳配体和反应条件，将这些负载的铜纳米粒子转化为高化学和立体选择性催化剂，用于制备 Z-烯烃（共 23 个实例）。例如，PCy 修饰的 Cu 纳米粒子半氢化 1-苯基-1-丙炔得到顺-β-甲基苯乙烯（20 巴 H，40°C），周转数和周转频率分别约为 540 和 1.9 分钟，在完全转化时具有 94%的选择性。
