Isolation of Planar Four-Membered Aromatic Systems by Using Confined Spaces of Cobalt Pentaaryl[60]fullerene Complexes
Isolation of Planar Four-Membered Aromatic Systems by Using Confined Spaces of Cobalt Pentaaryl[60]fullerene Complexes
复制标题
利用五芳基钴[60]富勒烯配合物的有限空间分离平面四元芳香体系
DOI：
10.1021/ja111474v
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发表时间：
2011
期刊：
影响因子：
--
通讯作者：
Y.
中科院分区：
文献类型：
--
作者：
Maruyama M.; Guo;J.-D.; Nagase;S.Nakamura;E.; Matsuo;Y.
CoE 3（E = S，Se）作为一类新型的中性闭壳芳香四元环体系，被构建在五芳基[60]富勒烯的碗状空间内. CoS 3（η5-C60 Ar 5）的X射线晶体学分析表明，CoS 3单元为平面结构，密度泛函理论计算表明其为芳香族6π电子体系.通过五芳基[60]富勒烯配体的空间保护对于芳香杂环丁烷钴的分离和表征是至关重要的。CoS 3单元的独特反应性通过6π-共轭的破坏与硫原子的提取来证明，从而提供二聚体[CoS 2（η5-C60 Ar 5）]2。这一工作为四元环体系的芳香性提供了新的认识，并推进了对芳香族有机金属化合物的理解。
As a new class of neutral closed-shell aromatic four-membered ring systems, CoE3(E = S, Se) was constructed inside the bowl-shaped space of pentaaryl[60]fullerene. X-ray crystallographic analysis of CoS3(η5-C60Ar5) revealed that the CoS3unit is planar, and DFT calculations suggested an aromatic 6π-electron system. Steric protection by the pentaaryl[60]fullerene ligand is critical for isolation and characterization of the aromatic hetero cobaltacyclobutane. Unique reactivity of the CoS3unit was demonstrated by disruption of 6π-conjugation with abstraction of the sulfur atom, affording a dimer, [CoS2(η5-C60Ar5)]2. This work provides new insight into the aromaticity of four-membered ring systems and advances the understanding of aromatic organometallic compounds.