By Hartmann H., et al. (eds.)
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Additional info for Houben-Weyl Methoden der organischen Chemie vol.E8a Hetarenes III, Part 1
Example text
A. DUNAND et al.
9. Absolute partial molar volumes, Vabs of [Ln(H2O)n]3+ in aqueous Ln(ClO4)3 solutions (u), compared with the calculated values for [Ln(H2O)8]3+ and [Ln(H2O)9]3+ indicated by the upper and lower solid lines, respectively. Interchange rate constants, 3+ ki, for the substitution of SO2À are shown as s, and water exchange 4 on [Ln(H2O)n] rate constants, (298 K) for [Ln(H2O)8]3+ are shown as . Activation volumes, ÁV z, are shown as j. The picture for water exchange on the lanthanide ions, conceived on the basis of structural and kinetic results, is as follows (Fig.
Nine coordination is favored for the larger ions and eight coordination for the smaller ones. The slightly less favored coordination state can, however, be similar to the transition state/intermediate in an exchange process. The energy barrier for a water exchange is therefore low, leading to very high reaction rates. A. DUNAND et al. FIG. 10. Possible mechanistic paths for water exchange on eight- and nine-coordinate lanthanides. predicted by this model: the a-activated mechanism for the small eightcoordinate ions, determined via the negative activation volumes, should be replaced by a d-activated mechanism for the larger nine-coordinate ions.