Free energies of transfer of complexes of the type MCl2py4 between pyridine and other solvent media

Solubility isotherms are reported for the NiCl2·4py, MnCl2·4py, and MnCl2·2py solid pyridinates in a number of pyridine+diluent mixtures at 25°C. Activity coefficients of the solvent components have been derived from the total vapor pressures measured by a static method. The standard free energies of transfer for the NiCl2py4 and MnCl2py4 complexes are the same, within the experimental error, in the pyridine+aprotic diluent mixtures, while marked differences are observed in the pyridine+chloroform mixtures. Marked deviations are observed for chloroform and 1,2-dichloroethane from a correlation between the standard free energy of transfer of the complexes, on one hand, and the Hildebrand's solubility parameter of the solvent, on the other, the latter correlation being roughly valid for aprotic solvents. The deviations are tentatively ascribed to hydrogen bond formation of the type H...π between the protic solvents and the coordinated pyridine molecules, enhanced by the d→π electron delocalization.