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Reaction of [GaBi3]2− with [Sm(C5Me4H)3] yielded the first protonated ternary intermetalloid clusters [Sm@Ga3− xH3−2 xBi10+ x]3− ( 1; x=0,1). The presence of the GaH bonds and the transfer of electrons and protons during the formation of 1 were elucidated by a combination of experimental and quantum chemical methods, thereby rationalizing the role of the solvent ethane-1,2-diamine as a Brønsted acid. As an organic by-product, we observed the previously unknown octamethylfulvene ( 2) upon CC coupling of (C5Me4H)−. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

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. A bismuth “ufosan” sighted: Upon activation of [K([2.2.2]crypt)]2(GaBi3)⋅en by the solvent pyridine, [K([2.2.2]crypt)]3(Bi11)⋅2 py⋅tol was obtained as the first structurally characterized homoatomic, polycyclic bismuth polyanion. It has the [P11]3− “ufosan” structure. Spectroscopy, spectrometry, and DFT studies were employed to understand the unprecedented reaction and its (by‐)products. [ABSTRACT FROM AUTHOR]