Chen Dafa, Hua Yuhui, Xia Haiping
Shenzhen Grubbs Institute and Guangdong Provincial Key Laboratory of Catalysis, Department of Chemistry, Southern University of Science and Technology, Shenzhen, People's Republic of China.
State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, People's Republic of China.
Chem Rev. 2020 Dec 9;120(23):12994-13086. doi: 10.1021/acs.chemrev.0c00392. Epub 2020 Oct 19.
Since the prediction of the existence of metallabenzenes in 1979, metallaaromatic chemistry has developed rapidly, due to its importance in both experimental and theoretical fields. Now six major types of metallaromatic compounds, metallabenzenes, metallabenzynes, heterometallaaromatics, dianion metalloles, metallapentalenes and metallapentalynes (also termed carbolongs), and spiro metalloles, have been reported and extensively studied. Their parent organic analogues may be aromatic, non-aromatic, or even anti-aromatic. These unique systems not only enrich the large family of aromatics, but they also broaden our understanding and extend the concept of aromaticity. This review provides a comprehensive overview of metallaaromatic chemistry. We have focused on not only the six major classes of metallaaromatics, including the main-group-metal-based metallaaromatics, but also other types, such as metallacyclobutadienes and metallacyclopropenes. The structures, synthetic methods, and reactivities are described, their applications are covered, and the challenges and future prospects of the area are discussed. The criteria commonly used to judge the aromaticity of metallaaromatics are presented.
自1979年金属苯被预测存在以来，金属芳香化学因其在实验和理论领域的重要性而迅速发展。目前，已报道并广泛研究了六种主要类型的金属芳香化合物，即金属苯、金属苯炔、杂金属芳香化合物、二价阴离子金属茂、金属戊搭烯和金属戊搭炔（也称为碳龙）以及螺金属茂。它们的母体有机类似物可能是芳香性的、非芳香性的，甚至是反芳香性的。这些独特的体系不仅丰富了芳香族化合物的大家族，而且还拓宽了我们的理解并扩展了芳香性的概念。本综述对金属芳香化学进行了全面概述。我们不仅关注了六类主要的金属芳香化合物，包括主族金属基金属芳香化合物，还关注了其他类型，如金属环丁二烯和金属环丙烯。描述了它们的结构、合成方法和反应活性，涵盖了它们的应用，并讨论了该领域的挑战和未来前景。介绍了常用于判断金属芳香化合物芳香性的标准。
