Homogeneous catalyst modifier for alkyne semi-hydrogenation: systematic screening in an automated flow reactor and computational study on mechanisms
Homogeneous catalyst modifier for alkyne semi-hydrogenation: systematic screening in an automated flow reactor and computational study on mechanisms
复制标题
炔烃半加氢均相催化剂改性剂：自动流动反应器中的系统筛选和机理计算研究
DOI：
10.1039/d2re00147k
复制
发表时间：
2022
影响因子：
3.9
通讯作者：
Cherkasov Nikolay
中科院分区：
文献类型：
--
作者：
Asano Shusaku;Adams Samuel J.;Tsuji Yuta;Yoshizawa Kazunari;Tahara Atsushi;Hayashi Jun-ichiro;Cherkasov Nikolay
通过向反应混合物中添加均相改性剂（或毒物）如喹啉，可以提高钯催化氢化的选择性。尽管通过改性剂（选择性催化剂中毒）来提高选择性已为人所知数十年，但我们对它们仍然知之甚少。最终，我们无法选择修改器来改进特定过程。在这项研究中，使用自动流动反应器系统筛选了 21 种用于炔烃半氢化的改性剂，这些改性剂具有不同的催化剂类型、反应时间和目标底物。所有研究变量的变化都会影响氢化活性和选择性，从而证实了多参数优化的有效性。 1,10-菲咯啉是超越喹啉的最佳选择性。密度泛函理论（DFT）计算表明，1,10-菲咯啉具有显着的吸附在催化剂不规则表面上的能力，从而引起不良反应。
The selectivity of palladium catalysed hydrogenation can be improved by adding a homogeneous modifier (or poison) such as quinoline to the reaction mixture. Although such selectivity improvement by modifiers (selective catalyst poisoning) has been known for decades, we still know little about them. We, ultimately, cannot select a modifier to improve a particular process. In this study, 21 types of modifiers are screened for the semi-hydrogenation of alkynes with varying catalyst type, reaction time, and target substrate using an automated flow reactor system. All of the studied variables changed affected hydrogenation activity and selectivity confirming the effectiveness of a multi-parameter optimization. 1,10-phenanthroline marked the best selectivity beyond quinoline. The density functional theory (DFT) calculations suggest that 1,10-phenanthroline has a remarkable ability to adsorb on the irregular surface of the catalyst that effects undesirable reaction.