Kinetic and thermodynamic characterization of thermal pyridine liberation-anation reactions of bis(2,3-alkanedione dioximato)dipyridinecobalt(III) iodide in the solid state.

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Thermodynamic and kinetic characterizations were carried out on the thermal, pyridine liberation-anation reactions, [CoIII(R,CH3-dioxH)2(py)2]I \oversetΔ→ [CoIII(R,CH3-dioxH)2(py)I]+py↑.* These occurred endothermally in the solid state of the complexes. The ΔH values of the reactions were determined. A large increment in the entropy was found to be indispensable for the progress of the reactions; it could be brought about by the liberation of gaseous pyridine from the solid system of the complexes. The kinetic analyses revealed that the reaction rates were increased by the substitution of R with the longer-carbon-chain alkyl groups. The activation enthalpies and activation free energies were shown to be decreased by the above substitutions. The CoIII-pyridine bond was observed to be weakened by the electron-donating inductive effect of R to the central cobalt atom and by the steric interference of R toward axial pyridine coordination.
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