Cooperative Reactivity in Carbometalated Pincer-Type Complexes Possessing an Appended Functionality,ACS Catalysis

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Cooperative Reactivity in Carbometalated Pincer-Type Complexes Possessing an Appended Functionality
ACS Catalysis ( IF 11.3 ) Pub Date : 2019-12-31 , DOI: 10.1021/acscatal.9b04882
Ajeet Singh ₁ , Dmitri Gelman _{1,

2}

Affiliation

Unlike traditional catalysis, where ligands only pass stereoelectronic information to the metal center, ligand–metal cooperative catalysis deals with noninnocent ligands that take an active part in facilitating reaction pathways. After the pioneering studies of Fryzuk, who described the noninnocent behavior of the amine-based aliphatic pincer ligands, and of Milstein, who discovered the dearomative cooperation mechanism in pyridine-based pincer systems, this concept also became prevalent in the context of pincer complexes. Many excellent reviews have dealt with these aspects of heteroatom-based pincer compounds. Nevertheless, this perspective aims to focus on recent developments in the chemistry and catalytic applications of the carbometalated pincer ligands for which noninnocent behavior is rarely observed, and especially those applications incorporating an appended functionality that can interact with the catalytic center. Combining the concepts of robust carbometalated pincer complexes and cooperative mechanisms highlighted by modulation of the secondary coordination sphere provides a “second wind” for this powerful family of organometallic compounds.

中文翻译：

具有附加功能的碳金属钳型配合物中的协同反应性

与传统的催化作用不同，传统的催化作用是配体仅将立体电子信息传递到金属中心，而配体-金属的协同催化作用则是对非纯配体的反应，它们在促进反应途径中起着积极的作用。在Fryzuk（描述了胺基脂肪族钳子配体的非无害行为）和Milstein（在吡啶基钳子系统中发现脱芳香合作机制）的开创性研究之后，这一概念在钳子复合物的背景下也变得很普遍。关于杂原子基钳子化合物的这些方面，许多出色的评论。不过，这种观点旨在关注碳金属化钳形配体在化学和催化应用方面的最新进展，这种情况很少观察到无毒行为，特别是那些包含可以与催化中心相互作用的附加功能的应用。将健壮的碳金属钳状配合物的概念与通过二级配位球的调制突出显示的协同机制相结合，为这种强大的有机金属化合物家族提供了“第二次动力”。

更新日期：2019-12-31

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