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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] · 8 NH3 (1) one ZnPh2 molecule and one H atom are bound to opposite, significantly elongated edges of a distorted Ge4 tetrahedron.
The new [SnBi3]5- polyanion is obtained by the reaction of K3Bi2 with K4Sn9 or K12Sn17 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.
Reactions of silylated clusters [Ge {Si(TMS) } ]? or [Ge {Si(TMS) } ]2? with dialkylhalophosphines R PCl (Cy, iPr, tBu) 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.
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