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Donor‐Acceptor Complexes of Tellurium Polycationic Clusters with Cyanogen
Author(s) -
Beck Johannes,
Zink Marcus
Publication year - 2009
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.200801422
Subject(s) - cyanogen , chemistry , yield (engineering) , tellurium , molecule , crystallography , chalcogen , octahedron , cluster (spacecraft) , crystal (programming language) , crystal structure , inorganic chemistry , organic chemistry , materials science , computer science , programming language , metallurgy
The reactions of cyanogen with Te 6 [AsF 6 ] 4 and Te 4 [AsF 6 ] 2 in SO 2 solutions yield Te 6 [AsF 6 ] 4 ·1.5C 2 N 2 ( 1 ) and Te 4 [AsF 6 ] 2 ·C 2 N 2 ( 2 ) as red crystals in quantitative yield. The complexes 1 and 2 are also generated in moderate yield by the reaction of Te, AsF 5 and C 2 N 2 in liquid SO 2 , but by‐products are formed. These reactions show the ability of cyanogen to act as a donor towards tellurium polycations. In the crystal structures, discrete octahedral [AsF 6 ] – ions are present and linear cyanogen molecules, which coordinate the tellurium atoms of the polycations η 2 by both nitrogen atoms. In the crystal structure of 1 , the trigonal‐prismatic Te 6 4+ clusters are bridged by cyanogen molecules to one‐dimensional zig‐zag chains. The crystal structure of 2 contains square‐planar Te 4 2+ clusters, which are bridged by cyanogen molecules to two‐dimensional sheets. The complexes 1 and 2 represent the first chalcogen polycationic cluster compounds containing a nitrogen ligation. The new compounds are unstable with respect to loss of cyanogen but stable under an atmosphere of C 2 N 2 . The Raman spectra of 1 and 2 were investigated and assigned. A serviceable and convenient way to handle air‐sensitive and cold liquids by a transfer needle technique is described.