Open AccessClusters of the Heavier Elements of Main Groups 14–16: A Novel Synthetic Route for Polyanions in Molten Crown Ether
Author(s) -
Thomas F. Fässler,
Roald Hoffmann
Publication year - 1998
Publication title -
chimia
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.387
H-Index - 55
eISSN - 2673-2424
pISSN - 0009-4293
DOI - 10.2533/chimia.1998.158
Subject(s) - crown ether , chemistry , crown (dentistry) , ethylenediamine , solvent , ion , 18 crown 6 , base (topology) , crystallography , inorganic chemistry , materials science , organic chemistry , mathematical analysis , mathematics , composite material
A novel procedure allows the synthesis of homoatomic polyanions directly from the elements E (E = Sn, As, Sb, Te) in molten A/18-crown-6 as reaction medium (A = K, Rb) at temperatures between 40 and 80° [1]. The reactions are carried out by adding E to mixtures of A and 18-crown-6 that proved to form stable melts under these conditions. Further work off using ethylenediamine or DMF as solvent yielded single crystals of the following compounds: [K(18-crown-6)]4Sn9 (1), [K(18-crown-6)]3KSn9·en (2), [K(18-crown-6)]3As7 (3), [K([2.2.2]crypt)]2[K(18-crown-6)]Sb7·0.5en (4), [Rb(18-crown-6)]3Sb7 (5), [K(18-crown-6)]2Te4 (6), and [K(18-crown-6)]2Te4·en (7). In all compounds short contacts between the Zintl ions and A-atoms are observed. The influence of cation-anion interactions on the structure of these anions is discussed.