Polybismuthide Anions as Ligands: The Homoleptic Complex [(Bi 7 )Cd(Bi 7 )] 4− and the Ternary Cluster [(Bi 6 )Zn 3 (TlBi 5 )] 4−
| Autor: | Stefanie Dehnen, Werner Massa, Niels Lichtenberger |
|---|---|
| Rok vydání: | 2019 |
| Předmět: |
chemistry.chemical_classification
010405 organic chemistry General Chemistry Reaction intermediate 010402 general chemistry 01 natural sciences Catalysis 0104 chemical sciences Coordination complex Metal chemistry.chemical_compound Crystallography chemistry visual_art visual_art.visual_art_medium Cluster (physics) Molecule Reactivity (chemistry) Homoleptic Ternary operation |
| Zdroj: | Angewandte Chemie International Edition. 58:3222-3226 |
| ISSN: | 1521-3773 1433-7851 |
| DOI: | 10.1002/anie.201812473 |
| Popis: | 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. |
| Databáze: | OpenAIRE |
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