Dreyhsig Gesa H, Giulimondi Vera, Kleoff Merlin, Lanfredi Letizia, Fuchs Maxim, Limberg Niklas, Reimann Marc, Kaupp Martin, Pérez-Ramírez Javier, Riedel Sebastian
Institute of Chemistry and Biochemistry, Inorganic Chemistry, Freie Universität Berlin, Fabeckstr. 34/36, 14195, Berlin, Germany.
ETH Zürich, Department of Chemistry and Applied Biosciences, Institute of Chemical and Bioengineering, Vladimir-Prelog-Weg 1, Zürich, 8093, Switzerland.
Adv Sci (Weinh). 2025 Aug;12(32):e03992. doi: 10.1002/advs.202503992. Epub 2025 Jun 10.
Herein, [NEtMe][PdCl] is reported as a highly active catalyst for the mercury-free hydrochlorination of acetylene to vinyl chloride, resulting from the combination of the bichloride-based ionic liquid [NEtMe][Cl(HCl)] with PdCl. Replacing gaseous HCl with the bichloride shifts the reaction in the liquid phase increasing the process safety by pressure reduction and achieves a turnover frequency of TOF = 110 mol h mol matching the productivity of state-of-the-art heterogeneous systems. Additionally, [NEtMe][PdCl] shows remarkable long-term stability and can be re-used over ten reaction cycles (200 h in total) without any problems due to its resistance to reduction by acetylene and coking as revealed by kinetic, theoretical, and spectroscopic investigations. Finally, initial catalytic studies demonstrate promising outcomes for applications of the bichloride-based ionic liquids with other noble metals, like platinum, if disproportionation phenomena, as observed for gold, do not occur.
在此，[NEtMe][PdCl]被报道为一种用于乙炔无汞氢氯化制氯乙烯的高活性催化剂，它是由基于二氯化物的离子液体[NEtMe][Cl(HCl)]与PdCl组合而成。用二氯化物替代气态HCl使反应转移至液相，通过减压提高了过程安全性，并实现了TOF = 110 mol h⁻¹ mol⁻¹的周转频率，与最先进的多相系统的生产率相当。此外，[NEtMe][PdCl]表现出显著的长期稳定性，由于动力学、理论和光谱研究表明其对乙炔还原和结焦具有抗性，因此可以在十个反应循环（总共200小时）中重复使用而没有任何问题。最后，初步催化研究表明，如果不像金那样出现歧化现象，基于二氯化物的离子液体与其他贵金属（如铂）的应用将有良好的结果。
