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Nobel-Metal Centered Polycations Au@Bi-10 (5+) or Pd@Bi-10 (4+) Embedded in Halogenido-Bismuthate(III)-Stannate(II) Frameworks
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Inorganic Chemistry.
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2009 (English)In: Zeitschrift für Anorganische und Allgemeines Chemie, ISSN 0044-2313, E-ISSN 1521-3749, Vol. 635, no 4-5, 743-752 p.Article in journal (Refereed) Published
Abstract [en]

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.

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2009. Vol. 635, no 4-5, 743-752 p.
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URN: urn:nbn:se:kth:diva-18389DOI: 10.1002/zaac.200900087ISI: 000265794100023Scopus ID: 2-s2.0-65249165456OAI: oai:DiVA.org:kth-18389DiVA: diva2:336436
Note
QC 20100525Available from: 2010-08-05 Created: 2010-08-05 Last updated: 2017-12-12Bibliographically approved

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