Biphasic Behaviors of Nd³⁺ Bound with Cyanex272, Cyanex301, and Cyanex302: A Molecular Dynamics Simulation Study

By means of molecular dynamics simulations, this work addresses the conformational flexibility and migration of trivalent neodymium (Nd³⁺) coordinated with three or six titled (thio)phosphinic ligands and shows that the fluxionality of the complexes enables them to adapt to the solvent environment during the migration. Cyanex272 forms a more compact complex than the other two types of ligands and screens more significantly the interaction between the water solvent and the metal ion in the complex, which weakens the detainment of the aqueous environment. This results in faster motion of the Nd(C272)₃ complex both in its translation and rotation than the other complexes when migrating to the organic phase and wins over the other two ligands in transporting the metal ions from the aqueous phase to the organic phase. Depending on the solvent environment, these complexes may take two types of conformations to balance the forces from the environment benefited from their fluxionality. The migration of the M:L = 1:6 complexes, Nd[H(C272)₂]₃ and Nd[H(C301)₂]₃, was also investigated. The rich presence of the alkyl groups in the complexes screens the influence of the aqueous environment and benefits the transportation of metal ions to the interface. This work is expected to contribute to the community of inorganic chemistry interested in the coordination chemistry of metal ions and their behaviors in the condensed phase.