Stability Series for the Complexation of Six Key Siderophore Functional Groups with Uranyl Using Density Functional...

Determining stability constants of uranyl complexes with the principal functional groups in siderophores and identifying stability series is of great importance to predict which siderophore classes preferentially bind to U^VI and, hence, impact uranium speciation in the environment. It also helps to develop resins for scavenging U^VI from aqueous solutions. Here, we apply a recently developed computational approach to calculate log β values for a set of geochemically relevant uranium organometallic complexes using Density Functional Theory (DFT). We determined the stability series for catecholate, hydroxamate, α-hydroxycarboxylate, α-aminocarboxylate, hydroxy-phenyloxazolonate, and α-hydroxyimidazole with the uranyl cation. In this work, the stability constants (log β₁₁₀) of α-hydroxyimidazolate and hydroxy-phenyloxazolonate are calculated for the first time. Our approach employed the B3LYP density functional approximation, aug-cc-pVDZ basis set for ligand atoms, MDF60 ECP for U^VI, and the IEFPCM solvation model. DFT calculated log β₁₁₀ were corrected using a previously established fitting equation. We find that the siderophore functional groups stability decreases in the order: α-hydroxycarboxylate bound via the α-hydroxy and carboxylate groups (log β₁₁₀ = 17.08), α-hydroxyimidazolate (log β₁₁₀ = 16.55), catecholate (log β₁₁₀ = 16.43), hydroxamate (log β₁₁₀ = 9.00), hydroxy-phenyloxazolonate (log β₁₁₀ = 8.43), α-hydroxycarboxylate bound via the carboxylate group (log β₁₁₀ = 7.51) and α-aminocarboxylate (log β₁₁₀ = 4.73). We confirm that the stability for the binding mode of the functional groups decrease in the order: bidentate, monodentate via ligand O atoms, and monodentate via ligand N atoms. The stability series strongly suggests that α-hydroxyimidazolate is an important functional group that needs to be included when assessing uranyl mobility and removal from aqueous solutions.