Matsumoto Hikaru, Hoshino Yu, Iwai Tomohiro, Sawamura Masaya, Miura Yoshiko
Department of Chemical Engineering, Faculty of Engineering, Kyushu University, 744 Motooka, Nishi-ku, Fukuoka, 819-0395, Japan.
Department of Applied Chemistry, Faculty of Engineering, Kyushu University, 744 Motooka, Nishi-ku, Fukuoka, 819-0395, Japan.
Chemistry. 2023 Oct 2;29(55):e202301847. doi: 10.1002/chem.202301847. Epub 2023 Aug 29.
Metal centers that can generate coordinatively unsaturated metals in accessible and stable states have been developed using synthetic polymers with sophisticated ligand and scaffold designs, which required synthetic efforts. Herein, we report a simple and direct strategy for producing polymer-supported phosphine-metal complexes, which stabilizes mono-P-ligated metals by modulating the electronic properties of the aryl pendant groups in the polymer platform. A three-fold vinylated PPh was copolymerized with a styrene derivative and a cross-linker to produce a porous polystyrene-phosphine hybrid monolith. Based on the Hammett substituent constants, the electronic properties of styrene derivatives were modulated and incorporated into the polystyrene backbone to stabilize the mono-P-ligated Pd complex via Pd-arene interactions. Through NMR, TEM, and comparative catalytic studies, the polystyrene-phosphine hybrid, which induces selective mono-P-ligation and moderate Pd-arene interactions, demonstrated high catalytic durability for the cross-coupling of chloroarenes under continuous-flow conditions.
通过具有复杂配体和支架设计的合成聚合物，已开发出能够生成处于可及且稳定状态的配位不饱和金属的金属中心，这需要合成方面的努力。在此，我们报告了一种制备聚合物负载膦 - 金属配合物的简单直接策略，该策略通过调节聚合物平台中芳基侧基的电子性质来稳定单 - P配位的金属。将三倍乙烯基化的PPh与苯乙烯衍生物和交联剂共聚，以制备多孔聚苯乙烯 - 膦杂化整体材料。基于哈米特取代基常数，调节苯乙烯衍生物的电子性质并将其引入聚苯乙烯主链，通过Pd - 芳烃相互作用来稳定单 - P配位的Pd配合物。通过核磁共振、透射电子显微镜和比较催化研究，诱导选择性单 - P配位和适度Pd - 芳烃相互作用的聚苯乙烯 - 膦杂化物在连续流动条件下对氯芳烃的交叉偶联表现出高催化耐久性。
