By Colin D. Hubbard Rudi Van Eldik
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Additional resources for Advances in Inorganic Chemistry: Inorganic Reaction Mechanisms (AIC) (Advances in Inorganic Chemistry)
If two carboxylate SOLVENT EXCHANGE ON METAL IONS 47 arms on the DOTA are replaced by H there is space for two to three H2O molecules in the ¢rst coordination shell of lanthanide complexes (235). 298 For the corresponding Eu3+ complex a stability constant K2”3 ¼ 4:0 was measured. The small increase in the water exchange rate of [Gd(DO2A)(H2O)2^3]+ (Table XVII) relative to that of [Gd(DOTA) (H2O)]À is a consequence of an unfavorable interplay of charge and hydration equilibria (235). A promising new class of stable Gd3+ complexes based onTREN-Me-3,2HOPO shows relatively fast water exchange rates.
4. 7. f By quantum chemical methods. A. DUNAND et al. the coordination of one £uoride or one hydroxide to U(IV) had no detectable e¡ect on the water exchange rate. ACKNOWLEDGEMENTS The authors gratefully acknowledge ¢nancial support from the Swiss National Science Foundation and the Swiss O⁄ce for Education and Science (COST Program). Furthermore, we wish to thank the large number of people who have contributed over the years to the work performed in Lausanne. V. A. DUNAND et al. A. DUNAND et al.
62 — for DTPA), and because of the much more open coordination site on [Eu(ODDA)(H2O)] allowing a second water molecule to approach the inner sphere. C. ACTINIDES Reports on studies of solvent exchange reactions on actinide compounds are very scarce. The most studied cation is UO2þ 2 . A. DUNAND et al. FIG. 12. X-ray structures of [Eu(DTPA)H2O]3À (left) and [Sr(ODDA)] (right). or four (HMPA) (264) solvent molecules in the ¢rst coordination shell. For complexes of the form [UO2S5]2+ (S = solvent) the exchange rates measured in inert diluents are nearly independent of concentration of S, and for S = TMP a positive ÁV z was measured (6).
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