Nobel-Metal Centered Polycations [Au@Bi-10](5 ) or [Pd@Bi-10](4 ) Embedded in Halogenido-Bismuthate(III)-Stannate(II) Frameworks

作者：Wahl Bernhard; Erbe Manuela; Gerisch Alexander; Kloo Lars; Ruck Michael^*

来源：Zeitschrift fur Anorganische und Allgemeine Chemie, 2009, 635(4-5): 743-752.

DOI：10.1002/zaac.200900087

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

The metal-rich halogenides AuBi14 delta Sn2 delta X21-delta (delta approximate to 0.4) and PdBi15 delta Sn2 delta X21-delta (delta approximate to 0.6) with X = Cl. Br were crystallized from melts of the metals and BiX3. In the rhombohedral structures (space group R (3) over bar: a approximate to 1050 pm: alpha approximate to 94 degrees), noble-metal centered pentagonal antiprisms [Au@Bi-19](5 ) resp. [Pd@Bi-19](4 ) are embedded in halogenidometallate frameworks (3)(x)[Bi-4 delta Sn2 delta X21-delta](5) resp. (3)[Bi-4 delta Sn2 delta X21-delta](4). Mixed Bi-III/Sn-II site occupation allows the framework to adopt different charges. Further exchange of (BiX3)-X-III against (SnX2)-X-II results in vacancies (delta) on the position of an isolated halide ion. In quantum chemical calculations the naked metal-clusters are found to be stable in D-5d symmetry with interatomic distances close to the observed ones. The significance of interactions between the Wade-type host cluster Bi-10(4 ) and the closed-subshell guest atoms Au or Pd-0 is reflected in the molecular orbital diagram, the population analyses and the ELI-D.

• 出版日期2009