Binding modes of oxalate in UO(2)(oxalate) in aqueous solution studied with first-principles molecular dynamics simulations. Implications for the chelate effect

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Buehl, Michael (författare)

(creator_code:org_t)

Royal Society of Chemistry (RSC), 2011
2011
Engelska.
Ingår i: Dalton Transactions. - : Royal Society of Chemistry (RSC). - 1477-9226 .- 1477-9234. ; 40:42, s. 11192-11199

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Abstract Ämnesord

Stäng

Car-Parrinello molecular dynamics simulations are reported for aqueous UO(2)(H(2)O)(n)(C(2)O(4)) (n = 3, 4), calling special attention to the binding modes of oxalate and the thermodynamics of the so-called chelate effect. Based on free energies from thermodynamic integration (BLYP functional), the kappa(1),kappa(1')-binding mode of the oxalate (with one O atom from each carboxylate coordinating) is more stable than kappa(2) (2 O atoms from the same carboxylate) and kappa(1) forms by 23 and 39 kJ mol(-1), respectively. The free energy of binding a fourth water ligand to UO(2)(H(2)O)(3)(kappa(1)-C(2)O(4)) is computed to be low, 12 kJ mol(-1). Changes of the hydration shell about oxalate during chelate opening are discussed. Composite enthalpies and free energies, obtained from both experiment and quantum-chemical modeling, are proposed for the formation of monodentate UO(2)(H(2)O)(4)(kappa(1)-C(2)O(4)). These data suggest that the largest entropy change in the overall complex formation occurs at this stage, and that the subsequent chelate closure under water release is essentially enthalpy-driven.

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