Molecular dynamics simulations on europium nitrate complexes with neutral organophosphorus ligands. What governs the stoichiometry and extractability of the complex?

Abstract

Molecular dynamics simulations have been performed in water on europium nitrate complexes Eu(NO3)3Lm with three neutral organophosphorus extractants (L = tri-n-butylphosphate (TBP), triphenylphosphine oxide (TPPO) and carbamoylphosphine oxide (CMPO)) in order to determine which factors govern the experimental 1∶3 stoichiometry in organic solution saturated with water. This stoichiometry was investigated by progressive saturation of the cation coordination sphere by L. Simulations without constraints lead to monodentate coordination of the NO3– anions to Eu3+, and to stoichiometries higher than 1∶3. When the NO3– ions are constrained to bind Eu3+ in a bidentate mode, complexes are stable up to 1∶3 stoichiometry with L = TPPO and CMPO. From the 1∶3 stoichiometry with bidentate nitrates, the interactions of the cation with water become repulsive, which facilitates the extraction from an aqueous to an organic phase. With TBP as ligand, 1∶4 stoichiometry cannot be precluded, but formation of this complex appears to be kinetically more difficult than for the 1∶3 complex.