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Reactions of Polyarsenides with Acetylene: Synthesis and Characterization of [Cs([18]crown‐6)] 2 As 7 C 14 H 11 ·6NH 3 and As 2 C 6 H 6
Author(s) -
Grassl Tobias,
Friedrich Ute,
Kaas Marina,
Korber Nikolaus
Publication year - 2015
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.201500112
Subject(s) - monoclinic crystal system , orthorhombic crystal system , substituent , chemistry , crystallography , acetylene , phenylacetylene , liquid ammonia , crystal structure , lone pair , ion , ammonia , stereochemistry , molecule , organic chemistry , catalysis
The reaction of Cs 3 As 7 with diphenylacetylene in the presence of 18crown‐6 in liquid ammonia results in the formation of the new compound [Cs(18crown‐6)] 2 As 7 C 14 H 11 · 6NH 3 , which crystallizes in black monoclinic crystals. It contains the first monosubstituated heptaarsenide anion with a hydrocarbon‐only substituent and theoretical calculations show a significant influence of the organic substituent on the electronic structure within the cage. The ( Z )‐1, 2‐diphenylethenyl‐heptaarsenide di‐anion can be seen as the first step towards the formation of 1, 2,3‐triarsolides. Further experiments regarding the reaction of Rb 3 As 11 and Cs 3 As 11 with acetylene gas in liquid ammonia reveal the formation of the diarsabarrelene As 2 C 6 H 6 , which crystallizes as colorless orthorhombic crystals. Calculations based on the structural data obtained by X‐ray crystallography show the electronically inert character of the arsenic lone pair.