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The Cluster Polymers $^{1}_{\infty}\rm [PtBi_{6}Cl_{10}]$ and $^{1}_{\infty}\rm [PtBi_{6}Br_{10}]$ : Synthesis, Thermochemistry, Crystal Structure and Chemical Bonding
Author(s) -
Steden Folker,
Schmidt Peer,
Wahl Bernhard,
Isaeva Anna,
Ruck Michael
Publication year - 2008
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.200700340
Subject(s) - crystallography , halogen , orthorhombic crystal system , bismuth , valence electron , chemistry , octahedron , cluster (spacecraft) , crystal structure , valence (chemistry) , atom (system on chip) , electron , physics , embedded system , alkyl , organic chemistry , quantum mechanics , computer science , programming language
The reaction of Bi, Pt and Bi X 3 ( X = Cl, Br) in an inert flux of Al X 3 yields black crystals of the subhalides PtBi 6 X 10 . The compounds can also be obtained from the cluster salts Bi 2/3 [PtBi 6 X 12 ] by abstracting ⅔ equivalents of Bi X 3 . Consequently, the formation of PtBi 6 X 10 is favored at higher temperatures when the vapor pressure p (Bi X 3 ) evolved from Bi 2/3 [PtBi 6 X 12 ] is high. In accordance with the experimental results a quantitative thermodynamic description of the system Bi/Pt/Cl is given. X‐ray diffraction on single‐crystals at 293 K revealed that the two PtBi 6 X 10 compounds crystallize isostructurally in the orthorhombic space group Pnma with a = 1631.4(1)/1682.39(5) pm, b = 2667.8(2)/2731.1(1) pm and c = 906.9(1)/978.30(4) pm for X = Cl/Br. The fundamental motif of the structure is the cuboctahedral [PtBi 6 X 12 ] cluster, in which the platinum atom centers an octahedron of bismuth atoms whose edges are bridged by twelve halogen atoms. By sharing two halogen atoms with in each case the two neighbors the clusters are concatenated into a cis‐trans chain $^{1}_{\infty}{\rm [PtBi_{6}}X{\rm _{8}}X\rm_{4/2}]$ . Despite the high metal content and their polymeric character, the compounds are semi‐conducting since all valence electrons are localized in the electron precise clusters.