Yoo Changho, Dodge Henry M, Miller Alexander J M
Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, NC 27516-3290, USA.
Chem Commun (Camb). 2019 Apr 25;55(35):5047-5059. doi: 10.1039/c9cc00803a.
Transition metal complexes that incorporate crown ethers into the supporting ligands have emerged as a powerful class of catalysts capable of cation-tunable reactivity. Cations held in the secondary coordination sphere of a transition metal catalyst can pre-organize or activate substrates, induce local electric fields, adjust structural conformations, or even modify bonding in the primary coordination sphere of the transition metal. This Feature Article begins with a non-comprehensive review of the structural motifs and catalytic applications of crown ether-containing transition metal catalysts, then proceeds to detail the development of catalysts based on "pincer-crown ether" ligands that bridge the primary and secondary coordination spheres.
将冠醚纳入配体的过渡金属配合物已成为一类强大的催化剂，具有阳离子可调的反应活性。处于过渡金属催化剂二级配位球中的阳离子可以预组织或活化底物、诱导局部电场、调整结构构象，甚至改变过渡金属一级配位球中的键合。这篇专题文章首先对含冠醚过渡金属催化剂的结构模式和催化应用进行了非全面的综述，然后详细介绍了基于连接一级和二级配位球的“钳形冠醚”配体的催化剂的发展情况。
