Rhodapentalenes: Pincer Complexes with Internal Aromaticity
Rhodapentalenes: Pincer Complexes with Internal Aromaticity
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DOI：
10.1016/j.isci.2019.08.027
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发表时间：
2019-08
期刊：
影响因子：
5.8
通讯作者：
Qingde Zhuo;Hong Zhang;Linting Ding;Jianfeng Lin;Xiaoxi Zhou;Yuhui Hua;Jun Zhu;H. Xia
中科院分区：
文献类型：
--
作者：
Qingde Zhuo;Hong Zhang;Linting Ding;Jianfeng Lin;Xiaoxi Zhou;Yuhui Hua;Jun Zhu;H. Xia
钳形复合体是一个非常多才多艺的家族，得益于它们的稳定性、多样性和可调性。许多化合物的外围含有芳香族有机环，芳香性对它们的稳定性和性质起着重要的作用，而它们的金属环核不是芳香族的。在这里，我们报告了罗达茂烯，它可以被视为夹杂化合物，其中的金属环核心显示出相当大的芳香性。罗达五烯表现出良好的热稳定性，尽管此类化合物中的Rh-碳键很脆弱。实验和计算研究表明，刚性CCC钳形结构的稳定性以及固有的芳香性对这些金属环型铑物种至关重要。在该体系中观察到典型的芳香族钳形化合物的金属-配体协同脱芳构化反应。这些发现为钳形化学提出了一个新的概念，即涉及金属轨道的内部芳香性，这将有助于探索结构基元的性质，并启发进一步的应用。
Pincer complexes are a remarkably versatile family benefited from their stability, diversity, and tunability. Many of them contain aromatic organic rings at the periphery, and aromaticity plays an important role in their stability and properties, whereas their metallacyclic cores are not aromatic. Herein, we report rhodapentalenes, which can be viewed as pincer complexes in which the metallacyclic cores exhibit considerable aromatic character. Rhodapentalenes show good thermal stability, although the rhodium-carbon bonds in such compounds are fragile. Experimental and computational studies suggest that the stabilization of rigid CCC pincer architectures together with an intrinsic aromaticity is vital for these metallacyclic rhodium species. Dearomatization-aromatization reactions, corresponding to metal-ligand cooperation of classical aromatic pincer complexes, were observed in this system. These findings suggest a new concept for pincer chemistry, the internal aromaticity involving metald-orbitals, which would be useful for exploiting the nature of construction motif and inspire further applications.