Yang Jingting, Xu Xin, Lin Zhenyang, Xie Zuowei
Department of Chemistry, State Key Laboratory of Synthetic Chemistry, The Chinese University of Hong Kong Shatin New Territories Hong Kong China.
Department of Chemistry, The Hong Kong University of Science and Technology Clear Water Bay Kowloon Hong Kong China.
Chem Sci. 2024 May 14;15(21):7943-7948. doi: 10.1039/d4sc02629b. eCollection 2024 May 29.
Though late transition metal aromatic metallabenzenes and related heteroatom-containing analogues have been well studied, the corresponding aromatic early transition metal complexes remain elusive. Herein, we demonstrate the synthesis of aromatic, planar, and delocalised organotantallapyridinium complexes a simple one-pot process by sequential treatment of tantalum methyl complex [η:σ-MeC(CH)(CBH)]TaMe with alkynes and isocyanide. Single-crystal X-ray analyses, NMR spectroscopic data and DFT calculations suggest that they are aromatic tantallapyridinium complexes, a class of long-sought-after molecules. This work would shed some light on the preparation of metallaaromatics involving early transition metals.
尽管晚期过渡金属芳香金属苯及其相关的含杂原子类似物已得到充分研究，但相应的芳香早期过渡金属配合物仍然难以捉摸。在此，我们展示了芳香、平面且离域的有机钽吡啶鎓配合物的合成——通过用炔烃和异氰化物依次处理钽甲基配合物[η:σ-MeC(CH)(CBH)]TaMe的简单一锅法。单晶X射线分析、核磁共振光谱数据和密度泛函理论计算表明它们是芳香钽吡啶鎓配合物，一类长期以来备受追寻的分子。这项工作将为涉及早期过渡金属的金属芳烃的制备提供一些线索。
