Syntheses, Structures and Reactivity of Novel Hydrates of ortho‐Sulfidostannte Salts

Abstract

By the synthesis of single-crystalline K ϩ , Rb ϩ , Cs ϩ and Ba 2ϩ salts of the ortho-sulfidostannate anion, using an efficient, three-step fusing/extraction/evaporation method, all of the "missing links" in the table of ortho-sulfidostannates that can be prepared by this method, were added. The resulting hydrate compounds have the general composition [A n (H 2 O) m ][SnS 4 ] and represent useful starting materials for the synthesis of transition metal complexes with [SnS 4 ] 4Ϫ groups as binary main group elemental ligands.

Synthesis and Crystal Structure of [Li8(H2O)29]­[Sn10O4S20]·2H2O

“…Unlike the quoted salt, that crystallizes in the monoclinic space group C 2/ c with crystallographic C 2 symmetry of the anions, 1 shows only crystallographic inversion symmetry and no crystallographic symmetry of the anions. This is in accordance with previous reports on symmetry reduction with increasing amount of solvent molecules per formula unit 18…”

New Lithium Chalcogenidotetrelates, LiChT: Synthesis and Characterization of the Li+-Conducting Tetralithium ortho-Sulfidostannate Li4SnS4

“…18,19 While the lighter homologous ternary systems Li 4 SiS 4 and Li 4−x Si 1−x P x S 4 have been synthesized and show similar conductivities to the corresponding germanates, 13,20 the influence of replacing germanium with the heavier homologue tin has not been investigated so far. On the thiostannate side, the only known compounds are the salt of the dinuclear anion, Li 4 Sn 2 S 6 ·8en, 21 and the salt of a super-tetrahedral cluster, [Li 8 22 In contrast to a variety of heavier homologues, 23 the ortho-thiostannate salt of the lightest alkali metal ion, Li 4 SnS 4 , has not been published to date neither in solvent-free form nor as any solvate. Motivated by the promising developments in inorganic Li + ion conductors, we intended to fill this gap by generating the so far missing, smallest unit and to determine its Li + ion conductivity.…”

Syntheses, Structures, and Comprehensive NMR Spectroscopic Investigations of Hetero‐Chalcogenidometallates: The Right Mix toward Multinary Complexes

“…This indicates the strong dependency of the equilibrium given in Equations (1) and (2) on different types of solvents due to different requirements for the stabilization of monomeric versus dimeric species by the solvent (see below). [13] and [ 4 ], respectively, one also observes the formation of mixed chalcogenidostannate anions. However, in the presence of sulfide ligands, the NMR spectra indicate the presence of three-coordinate meta-chalcogenidostannate anions [SnE 3Àx T x ] 2À as well as the four-coordinate ortho-chalcogenidostannate anions.…”