Add time:07/23/2019         Source:sciencedirect.com

The thermodynamic parameters for the dissociation in acetonitrile of the tris-trifluoromethanesulfonates of the heavier lanthanides according to the equilibrium Ln(tri)2 ++tri−⇌Ln(tri)3 (Ln=Tb–Lu; tri−=CF3SO3 −) are reported. Potentiometric, calorimetric, conductometric and FT-IR measurements show that in acetonitrile both Ln(tri)3 and Ln(tri)2 + form with n-butylamine at least four strong, mononuclear, successive complexes whose stability seems to be not very dependent upon the acceptor charge. The bonding of n-butylamine occurs with a preferential loss of solvent molecules from the coordination sphere of the metal ion rather than with release of triflate ions. The equilibria of formation of ternary complexes Ln(tri)nbutm(3−n)+ (but=n-butylamine; n=2 or 3; m=1–4) are qualitatively interpreted in terms of the different factors affecting the ion–ion and ion–dipole interactions. Apparent stability constants and the related thermodynamic values concerning the complexing ability toward n-butylamine of a system containing Ln(tri)3 and Ln(tri)2 + are given.

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