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The positive ÁV z values obtained for MeOH (98) and DMF (99) indicate that these solvent molecules exchange via a d-activation mode: molecules at the axial position can easily dissociate. 17O NMR studies on the aqua ion of Cu2+ allowed the determination of the water exchange rate and a characteristic time for the inversion of the tetragonal distortion ($ 5 ps at 298 K) (97 ). These results were based on the commonly accepted assumption that Cu2+, in analogy to the solid state, is also six-coordinate in aqueous solution (108).
The coordination numbers of the Ln3+ ions in water are now well established from di¡erent experimental techniques (214^221). The lighter La3+^Nd3+ ions are predominantly nine-coordinate, Pm3+^Eu3+ exist in equilibria between nine- and eight-coordinate states and the heavier Gd3+^Lu3+ are predominantly eight-coordinate. The change in coordination number is also re£ected in the absolute partial molar 0 volumes, Vabs , of several Ln3+ ions determined in aqueous solutions (222,223). For eight-coordinate heavy lanthanides (Gd3+ to Yb3+) rate constants for water exchange can be determined by oxygen-17 NMR relaxation and chemical shift measurements (224^226).
7 ^ ^ ^ D, Id D, Id D, Id D, Id D, Id D, Id Adapted from Refs. (56,257^259 ). a Six-coordinate ionic radii from Ref. (255). b First-order rate constant for the exchange of a particular coordinated solvent molecule (6). 2 for europium(II) (228). The water exchange rate measured on the divalent europium aqua ion is the fastest ever measured by 17O NMR (Table XVI) (2). C). The EXAFS study showed that an equilibrium between seven- and eight-coordinate states is possible which would explain the very low energy barrier between the transition state (eightcoordinate for an associative mechanism) and the ground state [Eu(H2O)7]2+ (228).