Abstract
Thermal NO dissociation reactions in the solid phase of mononitrosylcobalt(III) complexes with the formula, CoL 4NO (L 4 denotes tetradentate ligands such as bzacen, salen and its 5-NO 2, 5-Cl, and 5-Me derivatives 2 2 The following abbreviations are used in this paper; bzacen is N,N′-ethylenebis(2-benzoyl-1-methylethylideneaminato); salen, N,N′-ethylenebis(salicylidenaminato); 5-NO 2-, 5-Cl-, and 5-Me-salen are N,N′-ethylenebis(5-nitro-, 5-chloro-, and 5-methylsalicylideneaminato), respectively. ) have been investigated by means of TG, DSC, and pyrolysis gas chromatographic analyses. The complexes eliminated one mole of NO per mole in the 160–300°C range and reproduced CoL 4 complexes which possessed X-ray diffraction patterns similar to those of authentic CoL 4 complexes. The kinetic analyses indicated that the NO dissociation process followed a first-order equation; the activation enthalpy values were 120–124 kJ mol −1, being invariable irrespective of the nature of L 4. The values of heat of NO dissociation, determined by the DSC method were in the range 40–50 kJ mol −1. From these thermochemical data and the data of heat of solution of NO, the NO dissociation energies in solution were calculated to be 52–61 kJ mol −1. The thermal data were discussed in terms of the nature of the CoNO bond.
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