Polybismuthide Anions as Ligands: The Homoleptic Complex [(Bi7)Cd(Bi7)]4− and the Ternary Cluster [(Bi6)Zn3(TlBi5)]4−

We present the results from a reactivity study of the binary anion (TlBi3)2– towards Group 12 metal compounds MPh2 (M = Zn, Cd, Hg) in order to get access to coordination compounds of polycyclic polypnictide molecules like Bi73– or Bi113–. The coordination chemistry of these polybismuthide cages has been unprecedented to date, while it has been known for a long time for the lighter Group 15 anions Pn73– (Pn = P, As, Sb). The use of (TlBi3)2–, previously shown to release Tl under certain conditions in‐situ, resulted in the formation of the first heterometallic polyanion in which a nortricyclane‐type polybismuthide coordinates a transition metal atom, [(Bi7)Cd(Bi7)]4−. Reactions with the lighter group 12 metal precursor yielded the uncommon ternary cluster [(Bi6)Zn3(TlBi5)]4−, most likely representing a reaction intermediate, and at the same time hinting at the formation of the nortricyclane‐shaped cage. Quantum chemical studies provide a deeper insight into stability trends of the [(E7)M(E7)]4− anion family and reveal a complex bonding situation in [(Bi6)Zn3(TlBi5)]4−, which features both localized and multicenter bonding.

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