Cs₁₀Tl₆SiO₄, Cs₁₀Tl₆GeO₄, and Cs₁₀Tl₆SnO₃ – First Oxotetrelate Thallides, Double Salts Containing “Hypoelectronic” [Tl₆]^6– Clusters

Abstract

Cs 10 Tl 6 TtO 4 (Tt = Si, Ge) and Cs 10 Tl 6 SnO 3 were synthesized by the reaction of appropriate starting materials at 623-673 K, followed by fast cooling or quenching to room temperature, in arcwelded tantalum ampoules. According to single-crystal X-ray analyses, the compounds crystallize in new structure types (Cs 10 Tl 6 TtO 4 (Tt = Si, Ge), P2 1 /c and Cs 10 Tl 6 SnO 3 , Pnma), consisting of [Tl 6 ] 6clusters, which can be characterized as distorted octahedra compressed along one of the fourfold axes of an originally unperturbed octahedron, and [SiO 4 ] 4-, [GeO 4 ] 4or [SnO 3 ] 4anions. The oxotetrelate thallides can be regarded as "double salts", which consist of Cs 6 Tl 6 on one side and respective oxosilicates, -germanates and -stannates on the other, * Prof. Dr. M. Jansen

Synthesis and characterization of ternary trielides Na7KTr4 [Tr=In or Tl] including [Tr4]8− Tetrahedra

“…[50][51][52][53][54][55][56][57][58] Investigations on the incorporation of different, closed shell complex anions into the alkali metal -triel system allowed for the observation of isolated hypoelectronic [Tr 6 ] 6À or [Tr 11 ] 7À indium and also thallium clusters. [59][60][61][62] Besides that, isolated indium [In 5 ] clusters are reported in (Ba 6 N)[In 5 ] [63] and in the more complex (Ba 38 N 18 )[In 5 ] 2 [In 8 ], [64] where next to the [In 5 ] clusters also [In 8 ] clusters are present. Further, tetrahedral [In 4 ] subunits are observed in Tm 4 IrIn 4 , Lu 4 PtIn 4 , Gd 5 RhIn, [65][66][67] (A 19 N 7 )[In 4 ] 2 (A = Sr, Ca) [68] and Na 2 In.…”

“…Indium is located at the borderline between thallium and the lighter group 13 elements [50–58] . Investigations on the incorporation of different, closed shell complex anions into the alkali metal ‐ triel system allowed for the observation of isolated hypoelectronic [ Tr 6 ] 6− or [ Tr 11 ] 7− indium and also thallium clusters [59–62] . Besides that, isolated indium [In 5 ] clusters are reported in (Ba 6 N)[In 5 ] [63] and in the more complex (Ba 38 N 18 )[In 5 ] 2 [In 8 ], [64] where next to the [In 5 ] clusters also [In 8 ] clusters are present.…”

Endohedral Ten‐Vertex Clusters [Ga@Tl10]8− in the Mixed Trielides A8GaTl10 (A=K, Rb, Cs)

“…The octahedral clusters [Tl 6 ] 6− ( n =6) in the binary thallides KTl [44] and CsTl [60] as well as in ‘double salts’ with several other anions (e. g. Cs 12 [Tl 6 ][O] 3 , [57] K 10 [Tl 6 ][O] 2 [61] or Cs 10 [Tl 6 ][SiO 4 ]) [62] are strongly compressed along one four‐fold axis, so that they can be regarded as four distorted tetrahedra (4 T) sharing one (elongated) edge and four faces (cf. discussion and Figures in Ref.…”

“…discussion and Figures in Ref. [61,62]). The only indium cluster of this type, present in Cs 22 [In 6 ][SiO 4 ] 4 , [63] is even more distorted, in this case towards three face-sharing tetrahedra only.…”

[Tl7]7– Clusters in Mixed Alkali Metal Thallides Cs7.29K5.71Tl13 and Cs3.45K3.55Tl7

“…13,14 In general, [Tl 6 ] 6− octahedra are obtained in different binary and ternary materials, e.g., A 10 Tl 6 O 2 (A = K, Rb), 24 Cs 10 Tl 6 TtO 4 (Tt = Si, Ge), or Cs 10 Tl 6 SnO 3 . 25 Another very rare cluster unit is represented by the pentagonal bipyramidal [Tl 7 ] 7− . While heteroatomic pentagonal bipyramidal entities are known to be accessible using solution chemistry, 26,27 the homoatomic Tl 7 cluster represents a very rare structural moiety in the solid state.…”