Electrophilic aromatic substitution (EAS) reactions are widely regarded as characteristic reactions of aromatic species, but no comparable reaction has been reported for molecules with Craig-Möbius aromaticity. Here, we demonstrate successful EAS reactions of Craig-Möbius aromatics, osmapentalenes, and fused osmapentalenes. The highly reactive nature of osmapentalene makes it susceptible to electrophilic attack by halogens, thus osmapentalene, osmafuran-fused osmapentalene, and osmabenzene-fused osmapentalene can undergo typical EAS reactions. In addition, the selective formation of a series of halogen substituted metalla-aromatics via EAS reactions has revealed an unprecedented approach to otherwise elusive compounds such as the unsaturated cyclic chlorirenium ions. Density functional theory calculations were conducted to study the electronic effect on the regioselectivity of the EAS reactions.

亲电芳香取代（EAS）反应被广泛认为是芳香族物质的特征反应，但尚未报道具有克雷格-莫比乌斯芳香性的分子的类似反应。在这里，我们展示了克雷格-莫比乌斯芳烃、奥斯马五烯和稠合奥斯马五烯的成功 EAS 反应。奥斯马戊烯的高反应性使其容易受到卤素的亲电攻击，因此奥斯马戊烯、奥斯马呋喃稠合的奥斯马戊烯和奥斯马苯稠合的奥斯马戊烯可以发生典型的 EAS 反应。此外，通过 EAS 反应选择性形成一系列卤素取代的金属芳族化合物，揭示了一种前所未有的方法来制备难以捉摸的化合物，例如不饱和环状氯鎓离子。进行密度泛函理论计算来研究电子对 EAS 反应区域选择性的影响。