Raman study of the coordination structure of a rare Earth-acetate complex in water.
The Raman spectra of aqueous LnCl(3) x 20H(2)O x CH3(C)OOLi (LnCl(3), rare earth chloride) solutions have been measured in the liquid state. The change of the Raman symmetric Ln(3+)-OH(2) stretching band (v(w)) showed that the decrease in the ionic radius of rare earth (Ln(3+)) ions induces a change in coordination number of the Ln(3+) ion. The two peaks at 946 and 958 cm(-1) of the C-C stretching band (v(CC)) of the acetate ion are assigned to the bidentate ligand and the polymeric chain structure, respectively. The coordination structure of the acetate ion to Ln(3+) ion prefers the bidentate ligand to the polymeric chain structure throughout the rare earth series. The fraction of the bidentate ligand increases with decreasing ionic radius of the Ln(3+) ion. On the basis of the analyses of the v(w) and v(CC) bands, the change in the coordination number of the Ln(3+) ion is mainly due to the structural change (from the polymeric chain structure to the bidentate ligand) of the Ln(3+)-acetate complex rather than a elimination of one water molecule. Our results show that the Ln(3+) ions tend to form the bidentate ligand rather than the divalent (M(2+)) ions.
Takekiyo
Takahiro
T
Department of Applied Chemistry, National Defense Academy, 1-10-20, Hashirimizu, Yokosuka, Kanagawa 239-8686, Japan. take214@nda.ac.jp
Yoshimura
Yukihiro
Y