Cation-Controlled Olefin Isomerization Catalysis with Palladium Pincer Complexes
Cation-Controlled Olefin Isomerization Catalysis with Palladium Pincer Complexes
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DOI：
10.1021/acs.organomet.2c00315
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发表时间：
2022-10
期刊：
影响因子：
2.8
通讯作者：
Alexandra H. Farquhar;Kristen E. Gardner;Sebastian Acosta-Calle;A. M. Camp;Chun-Hsing Chen;Alexander J. M. Miller
中科院分区：
文献类型：
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作者：
Alexandra H. Farquhar;Kristen E. Gardner;Sebastian Acosta-Calle;A. M. Camp;Chun-Hsing Chen;Alexander J. M. Miller
合成了一系列胺给体上不同取代基的钯(II)钳形配合物，并将其用于催化烯烃异构化反应。在钳形配体中安装大环可以实现阳离子可切换的位置烯烃异构化：仅用催化剂没有观察到反应，而在Li+盐存在下，异构化可以干净地进行。机理研究表明，具有可接近的烯烃结合部位的高度亲电的PD中心在催化中起着关键作用。
: A series of palladium(II) pincer complexes with different substituents on the amine donor has been prepared and studied in olefin isomerization catalysis. Installing a macrocycle into the pincer ligand enables cation-switchable positional olefin isomerization: no reaction is observed with the catalyst alone, while in the presence of Li + salts isomerization proceeds cleanly. Mechanistic studies implicate a key role of highly electrophilic Pd centers with accessible olefin binding sites in catalysis.