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Synthesis and Characterization of [Rb([18]crown‐6)] 3 As 15 Zn·4NH 3 and [Rb([2.2.2]crypt)] 4 Sb 14 Zn·8NH 3
Author(s) -
Kaas Marina,
Korber Nikolaus
Publication year - 2017
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.201700171
Subject(s) - chemistry , crystallography , triclinic crystal system , antimony , cationic polymerization , liquid ammonia , monoclinic crystal system , antimonide , stereochemistry , crystal structure , inorganic chemistry , ammonia , organic chemistry
The new compound [Rb([18]crown‐6)] 3 As 15 Zn · 4NH 3 was obtained by the reaction of Rb 3 As 7 , ZnPh 2 , [18]crown‐6, and [2.2.2]crypt in liquid ammonia. The black monoclinic crystals contain the (As 15 Zn) 3– anion, in which two As 7 3– cages are linked by an As–Zn unit. The anionic units are separated by cationic [Rb([18]crown‐6)] + units. The analogous reaction of Rb 3 Sb 7 , ZnPh 2 , [18]crown‐6, and [2.2.2]crypt yielded black triclinic crystals of the compound [Rb([2.2.2]crypt)] 4 Sb 14 Zn · 8NH 3 . This is the first antimony derivative with the ( E 14 Zn) 4– anionic motif, which consists of two nortricyclane like cages linked by a Zn atom. Quantum chemical calculations on the anionic units confirm that the electron density is mainly found at the periphery of the cluster system. This phenomenon is in accord with the observations already reported for the 1,2,3‐tripnicolides.