Abstract

The coordination chemistry of bidentate aminopyridinato ligands (ApH), in particular 2-aminopyridines, is a highly popular area of research. Due to easy accessibility and versatility, 2-aminopyridines have played a prominent role as alternatives to cyclopentadienyl ligands in coordination chemistry. Easily modifiable steric bulks and the ability for fine-tuning of electronic effects have allowed researchers to control not only the metal-to-ligand stoichiometry but also the properties of their metal complexes. Previously, ligand redistribution was frequently observed for ligands of small steric demands. Bulky aminopyridinato ligands refer to ligands that incorporate alkyl-substituted phenyl groups at the amine/amido nitrogen and at the sixth position of the pyridine ring. The steric crowding allowed the stabilization of transition metals in unusually low oxidation conditions. One of the remarkable developments, for example, is the stabilization of metal–metal quintuple bonds by these ligands, thus providing a diamagnetic platform to study such systems chemically. Application of metal aminopyridinates in homogeneous catalysis has also broadened considerably in recent years. This review provides a comprehensive account of advances made with such ligands since their development for main group and transition elements.

Graphic abstract

中文翻译：

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庞大的氨基吡啶甲酸酯与主族和过渡金属的配位化学

摘要

二齿氨基吡啶并配体（ApH），特别是2-氨基吡啶的配位化学是一个非常受欢迎的研究领域。由于容易获得且具有多功能性，因此2-氨基吡啶在配位化学中作为环戊二烯基配体的替代品发挥了重要作用。易于修改的空间体积以及微调电子效应的能力使研究人员不仅可以控制金属与配体的化学计量，还可以控制其金属配合物的性质。以前，对于空间要求小的配体，经常观察到配体的重新分布。大量的氨基吡啶并配体是指在胺/酰胺氮和吡啶环的第六位上掺入烷基取代的苯基的配体。空间拥挤使得过渡金属能够在异常低的氧化条件下稳定下来。例如，一项显着的发展就是通过这些配体稳定了金属-金属五重键，从而为研究此类系统提供了反磁性平台。近年来，金属氨基吡啶酸盐在均相催化中的应用也已大大扩展。这篇综述全面地介绍了自此类配体发展为主要基团和过渡元素以来所取得的进展。近年来，金属氨基吡啶酸盐在均相催化中的应用也已大大扩展。这篇综述全面地介绍了自此类配体发展为主要基团和过渡元素以来所取得的进展。近年来，金属氨基吡啶酸盐在均相催化中的应用也已大大扩展。这篇综述全面地介绍了自此类配体发展为主要基团和过渡元素以来所取得的进展。

图形摘要