A Highly Reduced Ni–Li–Olefin Complex for Catalytic Kumada–Corriu Cross-Couplings

The catalytic activity of a highly reduced Ni catalyst in the context of a Kumada–Corriu cross-coupling has been studied. This nickel complex is characterized by its high electron density, stabilized by simple olefin ligands in combination with two Li ions. Landmark reactivity has been found with this precatalyst which operates at cryogenic temperatures, thus allowing the presence of sensitive functionalities. Structural elucidation of oxidative addition intermediates and their reactivity suggest highly reduced species being operative in the C–C bond forming event.

本研究针对高度还原态镍催化剂在熊田-科里乌交叉偶联（Kumada–Corriu cross-coupling）反应中的催化活性展开了系统探究。该镍配合物具备高电子密度特性，其稳定性来源于简单烯烃配体与两枚锂离子的协同作用。该前催化剂可在低温条件下发挥催化活性，展现出具有里程碑意义的反应性能，能够兼容各类敏感官能团。对氧化加成（oxidative addition）中间体的结构解析及其反应性研究表明，高度还原态镍物种参与了本次碳-碳键形成（C–C bond forming event）过程。