Redox-active carborane clusters in bond activation chemistry and ligand design
Redox-active carborane clusters in bond activation chemistry and ligand design
复制标题
键活化化学和配体设计中的氧化还原活性碳硼烷簇
DOI：
10.1039/d3cc03011c
复制
发表时间：
2023
影响因子：
4.9
通讯作者：
Peryshkov, Dmitry V.
中科院分区：
文献类型：
--
作者：
Nussbaum, Bryce C.;Humphries, Amanda L.;Gange, Gayathri B.;Peryshkov, Dmitry V.
二十面体闭十二碳硼烷能够接受两个电子，打开形成双阴离子nido簇。这种转变可用于存储电子、驱动键激活或改变与金属阳离子的配位。在这篇专题文章中，我们介绍了每种应用的案例，其中碳硼烷的氧化还原活性促进了独特产品的生成。我们通过簇和外面取代基之间的共轭强调了外面取代基对产物反应性和稳定性的影响。此外，详细介绍了配体设计中氧化还原性质和碳硼烷簇几何形状的利用，无论是在低价配合物的稳定还是配体几何形状的调整方面。
Icosahedral closo-dodecaboranes have the ability to accept two electrons, opening into a dianionic nido-cluster. This transformation can be utilized to store electrons, drive bond activation, or alter coordination to metal cations. In this feature article, we present cases for each of these applications, wherein the redox activity of carborane facilitates the generation of unique products. We highlight the effects of exohedral substituents on reactivity and the stability of the products through conjugation between the cluster and exohedral substituents. Futher, the utilization of the redox properties and geometry of carborane clusters in the ligand design is detailed, both in the stabilization of low-valent complexes and in the tuning of ligand geometry.