THERMODYNAMIC AND STRUCTURAL STUDIES OF METAL COMPLEXES IN VARIOUS SOLVENTS

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Abstract
Complexation of various metal-ligand systems has been discussed from the view-point of solute-solvent and solvent-solvent interactions in pure solvents and their mixtures on the basis of thermodynamic and structural measurements. In water and dioxane-water mixtures, it was suggested that the solvation structure in the secondary shell of ionic species significantly changes by adding dioxane to water due to the formation dioxane-water associates in the bulk. It was found that 1,10-phenanthroline formed its stacked species, such as [H(phen)2]+ and (phen)2, in water, but the species hydrophobically associated disappeared in dioxane-water mixtures due to breaking of the hydrogen-bonded structure of water. Complexation of Zn(II), Cd(II) and Hg(II) ions with SCN− ions in water was discussed in relation to the structures of the complexes determined by X-ray diffraction, and NMR and Raman spectral measurements. The solvent effect on the complexation of Cu(II) with chloride ions in acetonitrile, N,N-dimethylformamide and their mixtures was found to be remarkable, which was well explained in terms of preferential solvation of N,N-dimethylformamide, i.e., the formation of [Cu(dmf n )]2+ (n=1–6), in acetonitrile.

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