Processes of Thermal Dissociation of Clathrates on the Base of Coordination Compounds

Inclusion compounds are very interesting materials for thermoanalytical investigations. Stable guest molecules are packed in the cages, channels or layers in the host matrix, thermal dissociation reactions are reversible and have the clear-cut stoichiometry. The clathrates with a matrix of coordination compounds (of the type MA₄X₂]·nA) were synthesized (M=transition metals; A=Py, 4-MePy; X=NO₃, NCS, NCO; n=0.67 or 1 or 2). Four Py or MePy molecules are tightly bound in the coordination sphere by M-N bonds and others are confined in the matrix cavities by van der Waals forces. Processes of thermal dissociation of the clathrates were studied. Q-thermogravimetry (for checking the stable intermediate phases) and the home-made gas-flow reactor (as EGA-device for kinetic studies) were used. The compensation dependence (lgA_i=aE_i+b) was observed for the most of clathrates series, it was explained by the identity of the reaction mechanism. This revised version was published online in August 2006 with corrections to the Cover Date.