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s — Structures of solvated metal ions and metal complexes in non-aqueous solvents have been investigated by means of X-ray diffraction and the results are discussed in connection with thermodynamic quantities and spectroscopic data of these species. Solvation structures of alkali metal ions with special reference to lithium ion in formarnide, of copper(ll) in N,N-dimethylformamide (DMF) and in DMF acetonitrile (AN) mixtures, and of cadmium(ll) ion in DMF are discussed. Chioro and bromo complexes of copper(ll) ion have been investigated in DMF, AN, DMF-AN mixthres and dimethyl sulfoxide (DMSO) solutions by spectrophotometric and calorimetric measurements, and the structure of the complexes with varying numbers of ligands is estimated. The X-ray diffraction analysis of the structures of the stepwise complexes has not been carried out in these solvents. Structural studies of copper(ll)-chrolo complexes in methanol by the X-ray diffraction and EXAFS methods and those of copper(ll)-bromo complexes in methanol and in AN by the EXAFS method have been carried out to obtain the average structure of mixtures of the complexes. The structure of the tetrathiocyanatocadmate(ll complex in DtvIF and DMSO has been compared with that in water. It has been found that the tetrathiocyanatocadmate(ll) complex has a regular tetrahedral structure and it has two N and two S atoms in water, while it contains three N and one S atoms in the first coordination sphere in DMF and DMSO.

Structural studies on solvation and complexation of metal ions in nonaqueous solutions