Journal
INORGANIC CHEMISTRY
Volume 49, Issue 11, Pages 4928-4933Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ic9025624
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- Carl Trygger Foundation for Scientific Research
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The mechanism, rate constant, and activation parameters for the exchange between uranyl(VI)) oxygen and water oxygen in tetramethyl ammonium hydroxide solution, TMA-OH, have been determined using O-17 NMR magnetization transfer technique. In the concentration range investigated, the predominant complex is UO2(OH)(4)(2-). The experimental rate equation, rate = k(ex)[TMA-OH](free)[U(VI)](2)(total) indicates that the exchange takes place via a binuclear complex or transition state with the stoichiometry [(UO2(OH)(4)(2-))(UO2(OH)(5)(3-)]. The rate-determining step most likely takes place between the axial yl oxygens and the equatorial hydroxides. The experimental Gibbs energy of activation, Delta G(double dagger) = 60.8 +/- 2.4 kJ/mol is in good agreement with the value, Delta A(double dagger) approximate to Delta G(double dagger) = 52.3 +/- 5.4 kJ/mol, found by Buhl and Schreckenbach in a recent Car-Parrinello molecular dynamics study, indicating that their proposed shuttle mechanism may be applicable also on the proposed binuclear transition state.
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