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Releasing Antiaromaticity in Metal-Bridgehead Naphthalene
Journal of the American Chemical Society ( IF 15.0 ) Pub Date : 2021-09-17 , DOI: 10.1021/jacs.1c08106
Chun Tang 1, 2 , Yu Zhao 2, 3 , Jingjing Wu 2, 3 , Zhixin Chen 2 , Liu Leo Liu 1 , Yuan-Zhi Tan 2 , Jun Zhu 2, 3 , Haiping Xia 1, 2
Affiliation  

As a fundamental chemical property, aromaticity guides the synthesis of novel structures and materials. Replacing the carbon moieties of aromatic hydrocarbons with transition metal fragments is a promising strategy to synthesize intriguing organometallic counterparts with a similar aromaticity to their organic parents. However, since antiaromaticity will endow compound instability, it is a great challenge to obtain an antiaromatic organometallic counterpart based on such transition metal replacement in aromatic hydrocarbons. Here, we report an efficient aromaticity transformation on aromatic naphthalene through the bridgehead replacement of an osmium fragment, leading to the unprecedented synthesis of metal-bridgehead naphthalene featuring a highly twisted structure as confirmed by X-ray crystallography characterization. Such a twisted conformation works together with its phosphonium substituents to release the antiaromaticity in the planar conformation of the metal-bridgehead naphthalene. Our findings prove the bridgehead involvement of transition metals in unexpected aromaticity modifications and open an avenue for novel metal-bridgehead complexes.

中文翻译:

释放金属桥头萘中的反芳香性

作为一种基本的化学性质,芳香性指导新结构和材料的合成。用过渡金属片段代替芳烃的碳部分是合成具有与其有机母体相似芳香性的有趣有机金属对应物的有前途的策略。然而,由于反芳香性会赋予化合物不稳定性,因此基于芳香烃中的这种过渡金属置换来获得反芳香有机金属对应物是一个巨大的挑战。在这里,我们报告了通过桥头取代锇片段对芳族萘进行有效的芳香性转化,导致前所未有的金属桥头萘合成,其具有高度扭曲的结构,X 射线晶体学表征证实了这一点。这种扭曲的构象与其鏻取代基共同作用,以释放金属桥头萘平面构象中的反芳香性。我们的研究结果证明了过渡金属在意想不到的芳香改性中的桥头堡参与,并为新型金属桥头配合物开辟了道路。
更新日期:2021-09-29
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