Planar Möbius aromatic pentalenes incorporating 16 and 18 valence electron osmiums
Planar Möbius aromatic pentalenes incorporating 16 and 18 valence electron osmiums
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DOI：
10.1038/ncomms4265
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发表时间：
2014-02
影响因子：
16.6
通讯作者：
Congqing Zhu;Ming Luo;Qin Zhu;Jun Zhu;P. Schleyer;J. Wu;Xin Lu;H. Xia
中科院分区：
文献类型：
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作者：
Congqing Zhu;Ming Luo;Qin Zhu;Jun Zhu;P. Schleyer;J. Wu;Xin Lu;H. Xia
芳香性是闭路中具有离域电子的分子的高度稳定特征，通常仅限于具有 4n+2 个移动电子的“Hückel”系统。尽管莫比乌斯概念将芳香性原理扩展到 4n 移动电子物种，但罕见的已知例子具有复杂、扭曲的拓扑，其扩展不太可能。在这里，我们报告了奥斯马五烯的实现，这是第一个具有 16 和 18 价电子过渡金属的平面莫比乌斯芳香配合物。通过 X 射线结构、磁性和理论分析记录了这些奥斯马五烯的莫比乌斯芳香性，证明了母体奥斯马五烯的芳香性的基础。所有这些奥斯马五烯都是通过同一碳炔碳的面内π组分的亲电和亲核反应形成的，说明了两亲碳炔反应性，这在过渡金属化学中很少观察到。我们的研究结果极大地拓宽了莫比乌斯芳香性的范围，并为平面莫比乌斯芳香化学的推广开辟了前景。
Aromaticity, a highly stabilizing feature of molecules with delocalized electrons in closed circuits, is generally restricted to ‘Hückel’ systems with 4n+2 mobile electrons. Although the Möbius concept extends the principle of aromaticity to 4nmobile electron species, the rare known examples have complex, twisted topologies whose extension is unlikely. Here we report the realization of osmapentalenes, the first planar Möbius aromatic complexes with 16 and 18 valence electron transition metals. The Möbius aromaticity of these osmapentalenes, documented by X-ray structural, magnetic and theoretical analyses, demonstrates the basis of the aromaticity of the parent osmapentalynes. All these osmapentalenes are formed by both electrophilic and nucleophilic reactions of the in-plane π component of the same carbyne carbon, illustrating ambiphilic carbyne reactivity, which is seldom observed in transition metal chemistry. Our results widen the scope of Möbius aromaticity dramatically and open prospects for the generalization of planar Möbius aromatic chemistry.