Search

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]

Treatment of the binary Zintl anion (Sn2Bi2)2− with phosphines as mild oxidation agents in ortho‐difluorobenzene causes expansion to the new species (Sn4Bi4)2−, which crystallizes along with [K(crypt‐222)]+ cations (crypt‐222=4,7,13,16,21,24‐hexaoxa‐1,10‐diazabicyclo[8.8.8]hexacosane). The electron‐count and architecture of the anion are consistent with a Wade‐Mingos arachno‐type cluster, obtained in its minimum‐energy isomer according to DFT calculations (DOI: 10.1002/zaac.202300229)...By Yannick R. Lohse; Bastian Weinert; Benjamin Peerless and Stefanie DehnenReported by Author; Author; Author; Author [Extracted from the article]

Copyright of Nachrichten aus der Chemie is the property of Wiley-Blackwell and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

Abstract: This review article provides a survey of contemporary investigations on main group metal cluster formation, addressing homo‐ and heterometallic clusters (including small numbers of transition metal atoms), with or without an external ligand shell, thereby excluding clusters with non‐metal atoms as bridging ligands. Most of the studies reflected herein represent insights into the formation of intermediates from the starting material, or the final cluster formation from established intermediates. In rare cases, the entire process was suggested as a result of comprehensive, multi‐method elucidations. The article is to be understood as a state‐of‐the‐art report, as the subject matter is currently a rising field of research, which is still in its infancy, despite some early activities that date back to the 1980s. At the same time, the article intends to point toward both the importance and the feasibility of according studies, in order to encourage researchers to gain even more knowledge in this field. Only deep understanding of cluster formation will allow for design, and ultimately control, of their syntheses, with the long‐term goal of their optimization and purposeful application in catalysis or novel material synthesis. [ABSTRACT FROM AUTHOR]

2-Hydrazinobenzothiazole and 2-furaldehyde diethyl acetal were connected to complementarily functionalized tin sulfide clusters, with coupling of an acetal to a hydrazine-functionalized cluster being so far without precedence. Neither ethers nor an N,S combination of heteroatoms has so far been present in the ligand shell of tetrelchalcogenide clusters. The resulting cluster molecules are based on inorganic [Sn6S10] architectures and show different photoluminescence properties as a function of the attached ligands. [ABSTRACT FROM AUTHOR]

Reactions of the binary, pseudo-homoatomic Zintl anion (Pb2Bi2)2- with Ln(C5Me4H)3 (Ln=La, Ce, Nd, Gd, Sm, Tb) in the presence of [2.2.2]crypt in ethane-1,2-diamine/toluene yielded ten [K([2.2.2]crypt)]+ salts of lanthanide-doped semimetal clusters with 13 or 14 surface atoms. Single-crystal X-ray diffraction and energy-dispersive X-ray spectroscopy indicated the presence of the anions [Ln@Pb6Bi8]3-, [Ln@Pb3Bi10]3-, [Ln@Pb7Bi7]4-, or [Ln@Pb4Bi9]4- in single or double salts; the latter showed various ratios of the components in the solid state. The anions are the first ternary intermetalloid clusters comprising only elements of the sixth period of the periodic table, namely, Pb, Bi and lanthanides. This study, which was complemented by ESI mass spectrometry and 139La NMR spectroscopy in solution, rationalizes a continuous development of the ratio of 13:14-atom cages with the ionic radius of the embedded Ln3+ ion, which seems to select the most suitable cage type. Quantum chemical investigations helped to analyze this situation in more detail and to explain the observed subtle influence of the atomic radii. Magnetic measurements confirmed that the embedded Ln3+ ions keep their expected paramagnetic or diamagnetic nature. [ABSTRACT FROM AUTHOR]

Die Reaktion von [GaBi3]2− mit [Sm(C5Me4H)3] führte zur Bildung des ersten protonierten ternären intermetalloiden Clusters [Sm@Ga3−xH3−2xBi10+x]3− (1; x=0,1). Die Existenz von Ga ‐ H ‐ Bindungen und der Transfer von Elektronen und Protonen während der Bildung von 1 wurde durch Kombination verschiedener experimenteller und quantenchemischer Methoden beleuchtet, was auch die Rolle des Lösungsmittels 1,2 ‐ Diaminoethan als Brønsted ‐ Säure unterstrich. Als organisches Nebenprodukt wurde das bisher nicht bekannte Octamethylfulven (2) erhalten, das durch eine C ‐ C ‐ Kupplung aus (C5Me4H)− hervorging. Verlangen nach Protonen: Die Reaktion von [GaBi3]2− mit [Sm(C5Me4H)3] führte zur Bildung des ersten protonierten ternären intermetalloiden Clusters [Sm@Ga3−xH3−2xBi10+x]3− (x=0,1). Mittels experimenteller und quantenchemischer Analysen wurde die Existenz von Ga ‐ H ‐ Bindungen nachgewiesen und der Elektronen ‐ und Protonentransfer beim Bildungsprozess beleuchtet. [ABSTRACT FROM AUTHOR]

Copyright of Nachrichten aus der Chemie is the property of Wiley-Blackwell and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

Bisher galten polycyclische Bismut-Polyanionen als unbekannt, wodurch sich Bismut deutlich von seinen leichteren Homologen unterschied. Nach der Synthese von [K([2.2.2]crypt)]3(Bi11)⋅2 py⋅tol können wir nun jedoch das erste strukturell charakterisierte homoatomare, polycyclische Bismut-Polyanion vorstellen, welches die vom [P11]3− bekannte 'Ufosan'-Struktur aufweist. Es entsteht bei der Behandlung von [K([2.2.2]crypt)]2(GaBi3)⋅en mit Pyridin. Bei der Bildung der Titelverbindung zersetzt sich das binäre Zintl-Anion [GaBi3]2− unter oxidativer Kupplung von Pyridin-Molekülen und Freisetzung von H2. Die ungewöhnliche Reaktion und deren (Neben-)Produkte wurden mittels Spektroskopie, Spektrometrie und DFT-Studien untersucht. Alle Ergebnisse deuten darauf hin, dass die spezifischen Reaktionsbedingungen für die Bildung des [Bi11]3−-Anions essentiell sind - und dass generell nichts gegen die Bildung weiterer, auch größerer Bismut-Polyanionen spricht. [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]

Copyright of Angewandte Chemie is the property of Wiley-Blackwell and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

A series of luminescent polynuclear copper(I) phenyl thiolate clusters with functional groups in the organic ligand shell has been synthesized and characterized by single-crystal X-ray diffraction. Cluster compounds 1- 5 with Me2N groups bound to the phenyl thiolate are described and feature different nuclearities and core geometries. The heptanuclear compound 6, which contains both phenyl thiolate and Me3SiO functionalized phenyl thiolate ligands, is an unusual example of a mixed thiolate cluster and exhibits a core almost identical to that of 5. The optical properties of these compounds, which range from binuclear complexes with large Cu ···Cu distances to cluster molecules with seven copper atoms and relatively short Cu ···Cu distances, have been investigated. Compounds 1- 5 show strong absorption below 500 nm. The intense luminescence covers a wide range of the visible spectrum ( 1: green; 2 and 3: blue; 4 and 5: yellow). It seems likely that the optical transitions occur between orbitals of the thiol ligands and metal-centered orbitals; for the species with short Cu ···Cu distances ( 3- 5), these interactions cause a further redshift of the spectra. In addition, the influence of functional groups on optical absorption and emission is shown by the two Cu7 clusters 5 and 6, which differ solely in the electron-donating nature of their functional groups. [ABSTRACT FROM AUTHOR]

Copyright of Nachrichten aus der Chemie is the property of Wiley-Blackwell and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

[K([2.2.2]crypt)]3 [Sm@Ga2HBi11]0.9 [Sm@Ga3H3Bi10] 0.1·en·tol is synthesized from a mixture of [K([2.2.2]crypt)]2[GaBi3]·en and Sm(C5Me4H)3 in en (3 h in the dark) followed by layering with toluene (4 °C, 3 d, 10% yield). [ABSTRACT FROM AUTHOR]

The binary Zintl anion [GaBi3]2- decomposes under oxidative coupling of pyridine and release of H2 to form the polycyclic bismuth polyanion [Bi11]3-, which exhibits the [P11]3- 'ufosan' structure. [ABSTRACT FROM AUTHOR]

Bisher galten polycyclische Bismut ‐ Polyanionen als unbekannt, wodurch sich Bismut deutlich von seinen leichteren Homologen unterschied. Nach der Synthese von [K([2.2.2]crypt)]3(Bi11)⋅2 py⋅tol können wir nun jedoch das erste strukturell charakterisierte homoatomare, polycyclische Bismut ‐ Polyanion vorstellen, welches die vom [P11]3− bekannte “Ufosan” ‐ Struktur aufweist. Es entsteht bei der Behandlung von [K([2.2.2]crypt)]2(GaBi3)⋅en mit Pyridin. Bei der Bildung der Titelverbindung zersetzt sich das binäre Zintl ‐ Anion [GaBi3]2− unter oxidativer Kupplung von Pyridin ‐ Molekülen und Freisetzung von H2. Die ungewöhnliche Reaktion und deren (Neben ‐ )Produkte wurden mittels Spektroskopie, Spektrometrie und DFT ‐ Studien untersucht. Alle Ergebnisse deuten darauf hin, dass die spezifischen Reaktionsbedingungen für die Bildung des [Bi11]3− ‐ Anions essentiell sind – und dass generell nichts gegen die Bildung weiterer, auch größerer Bismut ‐ Polyanionen spricht. Ein Bismut ‐ „Ufosan“ wurde gesichtet: Nach Aktivierung von [K([2.2.2]crypt)]2(GaBi3)⋅en durch das Lösungsmittel Pyridin bildete sich [K([2.2.2]crypt)]3(Bi11)⋅py⋅tol, die erste strukturell charakterisierte Verbindung mit einem homoatomaren, polycyclischen Bismut ‐ Polyanion, in der [P11]3− ‐ „Ufosan“ ‐ Struktur. Spektroskopie, Spektrometrie und DFT ‐ Studien kamen zum Einsatz, um die unerwartete Reaktion und deren Produkte zu verstehen. [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]

Black, prismatic crystals of [K([2.2.2]crypt)]6{ [La@In2Bi11](μ-Bi)2 [La@In2Bi11]}·3en·3toluene are synthesized by addition of a suspension of [La(C5Me4H)3] (tris(tetramethylcyclopentadienyl)lanthanum) in toluene to a solution of [K([2.2.2]crypt)]2[InBi3]·en in en (vigorous stirring, 20 °C, 3 h, 11% yield). [ABSTRACT FROM AUTHOR]