Formation of [Bi₁₁]³⁻, A Homoatomic, Polycyclic Bismuth Polyanion, by Pyridine‐Assisted Decomposition of [GaBi₃]²⁻

Abstract

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.

Reprint of “Coordination chemistry of homoatomic ligands of bismuth, selenium and tellurium”

“…Except for Bi 2 4+ , all bismuth polycations are polyhedral clusters. Very recently, the first anionic bismuth polyhedron, the Zintl anion Bi 11 3− , has been isolated [16]. Besides the observation of anionic bismuth Zintl ions, such as Bi 7 3− , in the gas-phase were reported [17].…”

Chemical Bonding and σ-Aromaticity in Charged Molecular Alloys: [Pd2As14]4− and [Au2Sb14]4− Clusters

“…Anions with low nuclearities such as Sb n n − ( n  = 3, 5) and Bi n 3− ( n  = 2, 3) were isolated or stabilized by transition metals, suggesting the existence of [E n ] n − in solutions 16–18 . For higher nuclearities, Bi n 3− ( n =  7, 11) were obtained in the presence of Cr and Ga, respectively 19, 20 .…”

Between Localization and Delocalization: Ru(cod)2+ Units in the Zintl Clusters [Bi9{Ru(cod)}2]3− and [Tl2Bi6{Ru(cod)}]2−

“…[13] According to these,t he anion combines structural motifs that indicate an electronprecise situation, as is typical for non-deltahedral polypnictides, [8,12,14] with deltahedral three-center bonding indicating electron deficiency, which is quite rare in Bi chemistry. [13] According to these,t he anion combines structural motifs that indicate an electronprecise situation, as is typical for non-deltahedral polypnictides, [8,12,14] with deltahedral three-center bonding indicating electron deficiency, which is quite rare in Bi chemistry.…”