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Investigations on the Thermal Reactivity of Zn II and Cd II Selenocyanato Coordination Compounds
Author(s) -
Boeckmann Jan,
Reinert Thorben,
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.201100043
Subject(s) - pyridine , chemistry , zinc , reactivity (psychology) , cadmium , coordination complex , inorganic chemistry , crystal structure , thermal decomposition , medicinal chemistry , thermogravimetry , crystallography , metal , transition metal , organic chemistry , catalysis , medicine , alternative medicine , pathology
Reaction of zinc(II) and cadmium(II) selenocyanate with pyridine leads to the formation of new zinc(II) and cadmium(II) selenocyanato coordination compounds. The crystal structures of bis(selenocyanato‐ N )‐tetrakis(pyridine‐ N ) zinc(II) ( 1 ) and bis(selenocyanato‐ N )‐tetrakis(pyridine‐ N ) cadmium(II) ( 2 ) consist of discrete complexes in which the metal cations are octahedrally coordinated by two terminal N ‐bonded selenocyanato anions and four pyridine molecules. Investigations on the thermal degradation behavior of 1 and 2 using simultaneous differential thermoanalysis and thermogravimetry as well as X‐ray powder diffraction, IR‐ and Raman spectroscopy, prove that on heating the pyridine‐rich compounds 1 and 2 , a stepwise decomposition is observed, which leads to the formation of the pyridine‐deficient compounds bis(selenocyanato‐ N )‐bis(pyridine‐ N ) zinc(II) ( 3 ) and catena‐[bis(μ‐1,3‐selenocyanato‐ N , S )‐bis(pyridine‐ N ) cadmium(II)] ( 4 ) as intermediates. Whereas the octahedral coordination of the Cd II cations are unchanged in its pyridine‐deficient intermediate 4 , that is build up of polymeric chains, the crystal structure of compound 3 consists of tetrahedrally coordinated Zn II atoms, which are surrounded by two N ‐bonded selenocyanato anions and two pyridine ligands forming discrete complexes. The structures and the thermal reactivity are discussed and compared with that of related transition metal isothiocyanates and selenocyanates with pyridine.