Lu Zhengyu, Zhu Congqing, Cai Yuanting, Zhu Jun, Hua Yuhui, Chen Zhixin, Chen Jiangxi, Xia Haiping
State Key Laboratory of Physical Chemistry of Solid Surfaces and Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, P.R. China.
Department of Materials Science and Engineering, College of Materials, Xiamen University, Xiamen, 361005, P.R. China.
Chemistry. 2017 May 5;23(26):6426-6431. doi: 10.1002/chem.201700789. Epub 2017 Apr 7.
Metalla-aromatics are attractive species because they exhibit the properties of both organometallics and aromatics. Reported metal-bridged polycyclic aromatic complexes, as well as Möbius aromatic species, are still rare. Herein, we present the construction of two new metal-bridged polycyclic aromatic frameworks, α-metallapentalenofurans and lactone-fused metallapentalynes, by the reactions of osmapentalyne with terminal aryl alkynes in the presence of H O or HBF /H O, respectively. DFT calculations show that the α-metallapentalenofurans possess rare planar Craig-type Möbius aromaticity derived from the 11-center-12-electron d -p π-conjugation. This study offers a new route for the construction of polycyclic metalla-aromatics as well as planar Möbius aromatic species.
金属芳香化合物是引人注目的物种，因为它们兼具有机金属化合物和芳香化合物的性质。已报道的金属桥连多环芳烃配合物以及莫比乌斯芳香物种仍然很少见。在此，我们分别通过锇戊炔与末端芳基炔烃在H₂O或HBF₄/H₂O存在下的反应，展示了两种新型金属桥连多环芳烃骨架，即α-金属戊搭烯并呋喃和内酯稠合金属戊搭炔的构建。密度泛函理论计算表明，α-金属戊搭烯并呋喃具有源自11中心-12电子d-p π共轭的罕见平面克雷格型莫比乌斯芳香性。这项研究为构建多环金属芳香化合物以及平面莫比乌斯芳香物种提供了一条新途径。
