Zhang Yaowei, Han Feifei, Yin Zhihong, Cai Yapeng, Zhang Xiaoyan, Zhang Hong
College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, China.
School of Chemical Engineering, Dalian University of Technology, Dalian, China.
Nat Commun. 2025 Apr 16;16(1):3632. doi: 10.1038/s41467-025-58855-7.
Metallabenzenes are recognized as a unique class of aromatic compounds, not only of structural and theoretical interest but also as platforms to design powerful transformations. Here, we report the successful transmutation of a metallabenzene for pyridine synthesis. This 'metal-to-nitrogen swapping' process utilizes readily available ruthenabenzene phosphonium salts and commercially available 2-aminopyridines under mild conditions. The isolation of ruthena-azepines, containing a planar seven-membered aza-metallacycle, along with DFT calculations, supports the nitrogen insertion/metal deletion cascade driven by aromatization. Additionally, we investigate the tunable photophysical properties of the resulting pyridine phosphonium salts.
金属苯被认为是一类独特的芳香族化合物,不仅具有结构和理论研究价值,还可作为设计强大转化反应的平台。在此,我们报告了金属苯成功转化为吡啶的合成方法。这种“金属到氮的交换”过程在温和条件下利用了易于获得的钌苯鏻盐和市售的2-氨基吡啶。含有平面七元氮杂金属环的钌氮杂卓的分离以及密度泛函理论计算,支持了由芳构化驱动的氮插入/金属消除级联反应。此外,我们还研究了所得吡啶鏻盐的可调光物理性质。