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Syntheses, Structures, and Thermal Reactivity of New Zn II and Cd II Thio‐ and Selenocyanato Coordination Compounds
Author(s) -
Boeckmann Jan,
Reinert Thorben,
Jeß Inke,
Näther Christian
Publication year - 2011
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.201100111
Subject(s) - pyrazine , chemistry , thiocyanate , thermal decomposition , reactivity (psychology) , pyridine , thermogravimetry , crystallography , protonation , medicinal chemistry , stereochemistry , inorganic chemistry , organic chemistry , medicine , alternative medicine , pathology , ion
Reaction of Zn II and Cd II thiocyanate or selenocyanate with pyrazine leads to the formation of new Zn II and Cd II coordination compounds. The structures of [Zn(NCSe) 2 (pyrazine) 2 ] n ( 1A ), [Cd(NCS) 2 (pyrazine) 2 ] n ( 2A ) and [Cd(NCSe) 2 (pyrazine) 2 ] n ( 3A ) consist of octahedrally coordinated metal cations which are surrounded by two terminal N ‐bonded anions and two μ 2 ‐bridging pyrazine molecules. The metal cations are connected via the pyrazine ligands into layers, which are further linked by weak intermolecular S···S respectively Se···Se interactions. Investigations on the thermal degradation behavior of 1A , 2A , and 3A using simultaneous differential thermoanalysis and thermogravimetry as well as X‐ray powder diffraction, IR‐ and Raman spectroscopy prove that on heating, the pyrazine‐rich compound 1A decomposes in one step into zinc selenocyanate without the formation of a pyrazine‐deficient intermediate. In contrast, for compounds 2A and 3A a stepwise decomposition is observed, leading to the formation of the pyrazine‐deficient compounds [Cd(NCS) 2 (pyrazine)] n ( 2B‐I and 2B‐II ) and [Cd(NCSe) 2 (pyrazine)] n ( 3B ) as intermediates. The structures and the thermal reactivity are discussed and compared with that of related transition metal thiocyanates and selenocyanates with pyridine as N ‐donor ligand.