Fachbereich Chemie und Wissenschaftliches Zentrum für Materialwissenschaften, Philipps-Universität Marburg, Hans-Meerwein-Strasse, 35032 Marburg (Germany) http://www.uni-marburg.de/fb15/ag-dehnen.
Angew Chem Int Ed Engl. 2014 Apr 25;53(18):4704-8. doi: 10.1002/anie.201310456. Epub 2014 Mar 26.
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 "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 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 ion-and indicate the possibility of the generation and isolation of further, large bismuth polyanions.
迄今为止，多环铋多阴离子尚未被发现——因此可以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 的合成使我们能够呈现出第一个结构上被确定的同核、多环铋多阴离子，其表现出P11 “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 在吡啶分子的氧化偶联和 H2 的释放下分解，形成标题化合物。通过光谱、光谱和 DFT 研究调查了前所未有的反应、其产物和副产物。所有发现都表明特定的反应条件对于Bi11 离子的形成至关重要——并表明进一步生成和分离更大的铋多阴离子的可能性。
