Formation of [Bi(11)](3-) , a homoatomic, polycyclic bismuth polyanion, by pyridine-assisted decomposition of [GaBi(3)](2-).
Formation of [Bi(11)](3-) , a homoatomic, polycyclic bismuth polyanion, by pyridine-assisted decomposition of [GaBi(3)](2-).
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DOI：
10.1002/anie.201310456
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发表时间：
2014-04
影响因子：
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通讯作者：
B. Weinert;Armin R Eulenstein;Rodica Ababei;S. Dehnen
中科院分区：
文献类型：
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作者：
B. Weinert;Armin R Eulenstein;Rodica Ababei;S. Dehnen
到目前为止，多环铋聚阴离子尚不清楚，因此将铋与其较轻的同系物区分开来。然而，[K([2.2.2]crypt)]3 (Bi11 )⋅2 py⋅tol 的合成使我们能够提出第一个具有结构特征的同原子多环铋聚阴离子，它表现出 [P11 ](3-) “ufosan”结构。它是通过用溶剂吡啶处理 [K([2.2.2]crypt)]2 (GaBi3 )⋅en 得到的。二元Zintl阴离子[GaBi3](2-)在吡啶分子的氧化偶联下分解并释放H 2 ，形成标题化合物。通过光谱学、光谱测定法和 DFT 研究对这一前所未有的反应及其产物和副产物进行了研究。所有发现都揭示了特定的反应条件对于[Bi11](3-)离子的形成至关重要，并表明了进一步产生和分离大的铋聚阴离子的可能性。
Until now, polycyclic bismuth polyanions have not been known-thus discriminating bismuth from its lighter congeners. However, the synthesis of [K([2.2.2]crypt)]3 (Bi11 )⋅2 py⋅tol, allows us to present the first structurally characterized homoatomic, polycyclic bismuth polyanion, which exhibits the [P11 ](3-) "ufosan" structure. It was obtained upon treatment of [K([2.2.2]crypt)]2 (GaBi3 )⋅en with the solvent pyridine. The binary Zintl anion [GaBi3 ](2-) decomposes under oxidative coupling of pyridine molecules and release of H2 to form the title compound. The unprecedented reaction, its products and by-products were investigated by means of spectroscopy, spectrometry, and DFT studies. All findings reveal the specific reaction conditions to be crucial for the formation of the [Bi11 ](3-) ion-and indicate the possibility of the generation and isolation of further, large bismuth polyanions.