Gan Ming-Ming, Liu Ji-Quan, Zhang Le, Wang Yao-Yu, Hahn F Ekkehardt, Han Ying-Feng
Key Laboratory of Synthetic and Natural Functional Molecule Chemistry, College of Chemistry and Materials Science , Northwest University , Xi'an 710127 , P. R. China.
Institut für Anorganische und Analytische Chemie , Westfälische Wilhelms-Universität Münster , Corrensstraße 30 , D-48149 Münster , Germany.
Chem Rev. 2018 Oct 10;118(19):9587-9641. doi: 10.1021/acs.chemrev.8b00119. Epub 2018 Jul 5.
Although the coordination chemistry of N-heterocyclic carbenes (NHCs) with transition metals has been explored for half a century, only in the past ten years has the chemistry of metallosupramolecular assemblies based on poly-NHC ligands been studied more extensively. Remarkable discrete assemblies featuring poly-NHC ligands including two-dimensional metallacycles and three-dimensional metallaprisms/cages have since emerged. These assemblies are mostly obtained starting from various imidazolium or benzimidazolium salts. Driven by the increasing interest in new supramolecular architectures from carbon donor ligands, design, and construction of poly-NHC metal assemblies has become a rapidly growing area of research. The metal-carbene bond length is fixed to approximately 2.0 Å in linear NHC-M-NHC complexes. This allows the use of such complexes bearing olefin-substituted NHC ligands as templates for subsequent photochemical [2 + 2] cycloaddition reactions. The postassembly modification of such assemblies has been actively explored in recent years. In this review, we focus on the synthetic methods, characterization, structural features, and postassembly modifications of metallosupramolecular assemblies obtained from poly-NHC ligands.
尽管氮杂环卡宾（NHCs）与过渡金属的配位化学已被研究了半个世纪，但直到最近十年，基于多氮杂环卡宾配体的金属超分子组装体的化学才得到更广泛的研究。此后出现了以多氮杂环卡宾配体为特征的引人注目的离散组装体，包括二维金属环和三维金属棱柱/笼。这些组装体大多是从各种咪唑鎓盐或苯并咪唑鎓盐开始获得的。受对来自碳供体配体的新型超分子结构兴趣日益增加的驱动，多氮杂环卡宾金属组装体的设计和构建已成为一个迅速发展的研究领域。在直链NHC-M-NHC配合物中，金属-卡宾键长固定在约2.0 Å。这使得可以将带有烯烃取代的氮杂环卡宾配体的此类配合物用作后续光化学[2 + 2]环加成反应的模板。近年来，人们积极探索了此类组装体的组装后修饰。在这篇综述中，我们重点关注从多氮杂环卡宾配体获得的金属超分子组装体的合成方法、表征、结构特征和组装后修饰。
