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Reactions involving Zintl ions are typically carried out in N‐based solvents such as liquid ammonia (NH3(l)), ethane‐1,2‐diamine (en), pyridine (py), or acetonitrile (CH3CN). We are currently investigating the application of other solvents as alternatives. Herein, we present the synthesis of the (Sn4Bi4)2− anion, obtained as its [K(crypt‐222)]+ salt (crypt‐222=4,7,13,16,21,24‐hexaoxa‐1,10‐diazabicyclo[8.8.8]hexacosane), from reactions of the binary, pseudo‐tetrahedral Zintl anion (Sn2Bi2)2− in the presence of phosphines as oxidation agents in ortho‐difluorobenzene (o‐DFB). The cluster comprises 38 valence electrons, hence, represents an arachno‐type architecture according to Wade‐Mingos rules. Micro‐X‐ray fluorescence (μ‐XFS) spectroscopy rationalized the elemental composition of the anion, and quantum chemical studies served to compare the stability of possible structural isomers of the global minimum structure. [ABSTRACT FROM AUTHOR]

Reactions involving Zintl ions are typically carried out in N‐based solvents such as liquid ammonia (NH3(l)), ethane‐1,2‐diamine (en), pyridine (py), or acetonitrile (CH3CN). We are currently investigating the application of other solvents as alternatives. Herein, we present the synthesis of the (Sn4Bi4)2− anion, obtained as its [K(crypt‐222)]+ salt (crypt‐222=4,7,13,16,21,24‐hexaoxa‐1,10‐diazabicyclo[8.8.8]hexacosane), from reactions of the binary, pseudo‐tetrahedral Zintl anion (Sn2Bi2)2− in the presence of phosphines as oxidation agents in ortho‐difluorobenzene (o‐DFB). The cluster comprises 38 valence electrons, hence, represents an arachno‐type architecture according to Wade‐Mingos rules. Micro‐X‐ray fluorescence (μ‐XFS) spectroscopy rationalized the elemental composition of the anion, and quantum chemical studies served to compare the stability of possible structural isomers of the global minimum structure. [ABSTRACT FROM AUTHOR]

Binary molecular Zintl anions, which consist of either two different p-block atoms or one type of p- and d-block atoms each do not only exhibit exceptional cage-type architectures, but they have also served as starting materials for a variety of derivatives. Like their homoatomic cousins, they can be treated in regard of the structure-electron count relationship by application of either the 8 – N rule or Wade-Mingos rules. This review article provides a full collection of representative known examples and comments on the respective bonding situations and structures, also in the context of contemporary inorganic synthesis and materials chemistry. [ABSTRACT FROM AUTHOR]

Compounds containing molecular Zintl anions, which are homo- or heteroatomic, anionic molecules of groups 13–15, have served as starting materials for a variety of derivatives. Besides ligand attachment to these clusters or oxidative coupling, the cages were used as polyatomic ligands in transition metal complexes and as sources for intermetalloid clusters and nanostructured crystalline materials. This review article deals with the structures, bonding situations, electronic properties, and formation pathways of these nanoscale heterometallic clusters. [ABSTRACT FROM AUTHOR]

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]