Pincer and Pincer‐Type Complexes Applications in Organic Synthesis and Catalysis. Edited by Kálmán J. Szabó and Ola F. Wendt
Pincer and Pincer‐Type Complexes Applications in Organic Synthesis and Catalysis. Edited by Kálmán J. Szabó and Ola F. Wendt
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DOI：
10.1002/anie.201501805
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发表时间：
2015-04
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通讯作者：
K. Kirchner
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文献类型：
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作者：
K. Kirchner
过渡金属配合物是每个从事合成的化学家不可缺少的工具。理想情况下，任何金属介导的催化过程都应该是快速，清洁，高效和选择性的。当人们考虑到许多用于催化的过渡金属是稀有和/或昂贵的时，这些标准是特别重要的。修饰和控制过渡金属配合物性质的方法之一是使用合适的配体体系，如钳形配体。三齿钳形配体通常基于由中心中性或阴离子芳族主链组成的平面支架，其通过间隔物栓系到两个通常庞大的双电子供体基团。近年来，具有脂肪族主链的钳子也受到了相当大的关注。在这些配体家族中，空间、电子以及立体化学参数可以通过供体位点和/或间隔基处的取代基的修饰来操纵，从而允许合理和模块化设计的可能性，以产生用于具有高选择性的一系列化学转化的高活性催化剂。因此，钳配合物是重要的工具，在化学的各个领域有许多应用，包括催化，由于它们的稳定性，活性和可变性的组合。这本书包含11章，涉及过渡金属钳和钳型配合物的广泛的主题，如机械和合成研究，配体设计，在均相催化的新应用，和理论考虑。这些文章的作者都是各自领域的知名科学家和专家。在基础研究主题和其他主要强调应用的文章之间有一个很好的平衡。本书的内容在此简要概述。Gunanathan和Milstein综述了Ru钳形配合物催化合成酯、酰胺和肽的潜力。它们很好地证明了钳形平台提供了微调金属络合物的空间和电子性质的机会，并为金属-配体合作开辟了新的可能性。Campora和Melero专注于氧化还原过程在由带有几个阴离子钳形配体的Ni和Pd络合物催化的反应中的作用。他们强调了金属钳框架中涉及氧化还原变化的催化反应的有用性，其中包括Kharasch和Heck反应以及其他CNO 3 C和CNO 3 X键形成过程。摩尔和辛恰克描述了
Transition metal complexes are indispensable tools for every chemist engaged in synthesis. Ideally, any metalmediated catalytic process should be fast, clean, efficient, and selective. These criteria are especially important when one considers that many of the transition metals employed in catalysis are rare and/or expensive. One of the ways of modifying and controlling the properties of transition metal complexes is the use of appropriate ligand systems such as pincer ligands. A tridentate pincer ligand is typically based on a planar scaffold consisting of a central neutral or anionic aromatic backbone, which is tethered through spacers to two, usually bulky, two-electron donor groups. In recent years, pincers with aliphatic backbones have also received considerable attention. In these families of ligands, steric, electronic, and also stereochemical parameters can be manipulated by modifications of the substituents at the donor sites and/or the spacers, allowing the possibility of a rational and modular design to generate highly active catalysts for a range of chemical transformations with high selectivity. Accordingly, pincer complexes are important tools with numerous applications in various areas of chemistry, including catalysis, due to their combination of stability, activity, and variability.This book contains 11 chapters on a wide range of topics involving transition-metal pincer and pincer-type complexes, such as mechanistic and synthetic studies, ligand design, new applications in homogenous catalysis, and theoretical considerations. The articles are written by authors who are well-known scientists and experts in their respective fields. There is a good balance between articles on fundamental research topics and others where the main emphasis is on applications. The contents of the book are briefly summarized here. Gunanathan and Milstein review the potential of Ru pincer complexes for the catalytic synthesis of esters, amides, and peptides. They nicely demonstrate that the pincer platform offers the opportunity to fine-tune the steric and electronic properties of the metal complexes and open up new possibilities for metal–ligand cooperation. Campora and Melero focus on the role of redox processes in reactions catalyzed by Ni and Pd complexes bearing several anionic pincer ligands. They emphasize the usefulness of catalytic reactions involving redox changes in the metal–pincer framework, which includes Kharasch and Heck reactions as well as other CÀC and CÀX bondforming processes. Moore and Szymcak describe