Nobel-metal centered polycations [Au@Bi10]5+ or [Pd@Bi10]4+ embedded in halogenido-bismuthate(III)- stannate(II) frameworks

Publikation: Beitrag in FachzeitschriftForschungsartikelBeigetragenBegutachtung

Beitragende

  • Bernhard Wahl - , Technische Universität Dresden (Autor:in)
  • Manuela Erbe - , Technische Universität Dresden (Autor:in)
  • Alexander Gerisch - , Technische Universität Dresden (Autor:in)
  • Lars Kloo - , KTH Royal Institute of Technology (Autor:in)
  • Michael Ruck - , Professur für Anorganische Chemie (II) (AC2), Technische Universität Dresden (Autor:in)

Abstract

The metal-rich halogenides AuBi14-δSn 2+δX21-δ (δ ≈ 0.4) and PdBi 15-δSn1+δX21-δ (δ ≈ 0.6) with X = Cl, Br were crystallized from melts of the metals and BiX 3. In the rhombohedral structures (space group R3̄; a ≈ 1050 pm; α ≈ 94°), noble-metal centered pentagonal antiprisms [Au@Bi10]5+ resp. [Pd@Bi10]4+ are embedded in halogenidonietallate frameworks 3 [Bi4-δSn2+δX 21-δ]5- resp. 3[Bi 5-δSn1+δX21-δ]4-. Mixed BiIII/Snπ site occupation allows the framework to adopt different charges. Further exchange of BiIIIX3 against SnIIX2 results in vacancies (δ) on the position of an isolated halide ion. In quantum chemical calculations the naked metal-clusters are found to be stable in D5d symmetry with interatomic distances close to the observed ones. The significance of interactions between the Wade-type host cluster Bi104+ and the closed-subshell guest atoms Au+ or Pd0 is reflected in the molecular orbital diagram, the population analyses and the ELI-D.

Details

OriginalspracheEnglisch
Seiten (von - bis)743-752
Seitenumfang10
FachzeitschriftZeitschrift fur Anorganische und Allgemeine Chemie
Jahrgang635
Ausgabenummer4-5
PublikationsstatusVeröffentlicht - Apr. 2009
Peer-Review-StatusJa

Externe IDs

ORCID /0000-0002-2391-6025/work/159171926

Schlagworte

ASJC Scopus Sachgebiete

Schlagwörter

  • Bismuth, Cluster compounds, Gold, Polycations, Quantum chemistry