NaTaP: A Ternary Sodium Phosphidotantalate Containing [TaP] Tetrahedra.

While lithium phosphides have been investigated intensively, very little is known about the corresponding sodium-based phosphides. Here, we report on the first ternary Na-Ta-P compound NaTaP, which is easily accessible via ball milling of the elements and subsequent annealing. The single crystal X-ray structure determination [monoclinic symmetry; space group 2/; and lattice parameters = 11.

Synthesis, Structure, Solid-State NMR Spectroscopy, and Electronic Structures of the Phosphidotrielates Li AlP and Li GaP.

The lithium phosphidoaluminate Li AlP represents a promising new compound with a high lithium ion mobility. This triggered the search for new members in the family of lithium phosphidotrielates, and the novel compounds Li AlP and Li GaP , obtained directly from the elements via ball milling and subsequent annealing, are reported here. It was unexpectedly found through band structure calculations that Li AlP and Li GaP are direct band gap semiconductors with band gaps of 3.

Solvate-Induced Semiconductor to Metal Transition: Flat [Bi ] Zigzag Chains in Metallic KBi⋅NH versus [Bi ] Helices in Semiconducting KBi.

Polymeric [Bi] in KBi⋅NH has planar zigzag chains with two-connected Bi atoms and metallic properties, whereas KBi, which has helical chains of Bi atoms, is semiconducting. The isomerization of the Bi chain is induced by solvate molecules. In the novel layered solvate structure uncharged [KBi] layers are separated by intercalated NH molecules.

Metallocages for Metal Anions: Highly Charged [Co@Ge ] and [Ru@Sn ] Clusters Featuring Spherically Encapsulated Co and Ru Anions.

Endohedral clusters count as molecular models for intermetallic compounds-a class of compounds in which bonding principles are scarcely understood. Herein we report soluble cluster anions with the highest charges on a single cluster to date. The clusters reflect the close analogy between intermetalloid clusters and corresponding coordination polyhedra in intermetallic compounds.

[(μ-H)(η-Ge)ZnPh], an edge-on protonated E cluster establishing the first three-center two-electron Ge-H-Ge bond.

The first example of a protonated and a rare example of a metal complex of the tetrahedral tetrel cluster anion [Ge4]4- was obtained from a solution of K6Rb6Ge17 in liquid ammonia in the presence of ZnPh2 and [18]crown-6. In [K([18]crown-6)][Rb([18]crown-6)]2[HGe4ZnPh2]·8NH3 (1) one ZnPh2 molecule and one H atom are bound to opposite, significantly elongated edges of a distorted Ge4 tetrahedron. DFT calculations confirm the experimentally found interatomic distances and reveal a structural proof of a three-center two-electron Ge-H-Ge bond.

[SnBi ] -A Carbonate Analogue Comprising Exclusively Metal Atoms.

The new [SnBi ] polyanion is obtained by the reaction of K Bi with K Sn or K Sn in liquid ammonia. The anion is iso(valence)electronic with and structurally analogous to the carbonate ion. Despite the high negative charge of the anion, the Sn-Bi bond lengths range between single and double bonds.

Derivatization of Phosphine Ligands with Bulky Deltahedral Zintl Clusters-Synthesis of Charge Neutral Zwitterionic Tetrel Cluster Compounds [(Ge{Si(TMS)})BuP]M(NHC) (M: Cu, Ag, Au).

Reactions of silylated clusters [Ge{Si(TMS)}] or [Ge{Si(TMS)}] with dialkylhalophosphines RPCl (Cy, Pr, Bu) at ambient temperature yield the first tetrel Zintl cluster compounds bearing phosphine moieties. Varying reactivity of the dialkylhalophosphines toward the silylated clusters is observed depending on the bulkiness of the phosphine's alkyl substituents and on the number of hypersilyl groups at the tetrel cluster. Reactions between phosphines with small cyclohexyl- (Cy) or isopropyl- (Pr) groups and the tris-silylated cluster [Ge{Si(TMS)}] yield the novel neutral cluster compounds [Ge{Si(TMS)}PR] (R: Cy (1), Pr (2)) with discrete Ge-P exo bonds.