Polybismuthide Anions as Ligands: The Homoleptic Complex [(Bi7)Cd(Bi7)]4− and the Ternary Cluster [(Bi6)Zn3(TlBi5)]4−
Dr. Niels Lichtenberger
Fachbereich Chemie und Wissenschaftliches Zentrum für Materialwissenschaften, Philipps-Universität Marburg, Hans-Meerwein-Straße 4, 35043 Marburg, Germany
Search for more papers by this authorProf. Dr. Werner Massa
Fachbereich Chemie und Wissenschaftliches Zentrum für Materialwissenschaften, Philipps-Universität Marburg, Hans-Meerwein-Straße 4, 35043 Marburg, Germany
Search for more papers by this authorCorresponding Author
Prof. Dr. Stefanie Dehnen
Fachbereich Chemie und Wissenschaftliches Zentrum für Materialwissenschaften, Philipps-Universität Marburg, Hans-Meerwein-Straße 4, 35043 Marburg, Germany
Search for more papers by this authorDr. Niels Lichtenberger
Fachbereich Chemie und Wissenschaftliches Zentrum für Materialwissenschaften, Philipps-Universität Marburg, Hans-Meerwein-Straße 4, 35043 Marburg, Germany
Search for more papers by this authorProf. Dr. Werner Massa
Fachbereich Chemie und Wissenschaftliches Zentrum für Materialwissenschaften, Philipps-Universität Marburg, Hans-Meerwein-Straße 4, 35043 Marburg, Germany
Search for more papers by this authorCorresponding Author
Prof. Dr. Stefanie Dehnen
Fachbereich Chemie und Wissenschaftliches Zentrum für Materialwissenschaften, Philipps-Universität Marburg, Hans-Meerwein-Straße 4, 35043 Marburg, Germany
Search for more papers by this authorGraphical Abstract
A coordination compound with intact Bi73− ligands, namely the homoleptic complex [(Bi7)Cd(Bi7)]4−, and the ternary cluster [(Bi6)Zn3(TlBi5)]4− were prepared through in situ degradation of the binary Zintl anion (TlBi3)2−. The compounds provide a glimpse into a possible formation pathway of the polycyclic polybismuthide, the follow-up chemistry of which has been unprecedented to date. Both title compounds were further studied by means of DFT methods.
Abstract
We present the results from a reactivity study of the binary anion (TlBi3)2− towards Group 12 metal compounds MPh2 (M=Zn, Cd, Hg) to gain access to coordination compounds of polycyclic polypnictide molecules such as 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 deeper insight into the 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 multi-center bonding.
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