Effects of coordinating heteroatoms on molecular structure, thermodynamic stability and redox behavior of uranyl(vi) complexes with pentadentate Schiff-base ligands

Abstract

Uranyl(VI) complexes with pentadentate N₃O₂-, N₂O₃- and N₂O₂S₁-donating Schiff base ligands, tBu,MeO–saldien–X²⁻ (X = NH, O and S), were synthesized and thoroughly characterized by ¹H NMR, IR, elemental analysis, and single crystal X-ray diffraction. The crystal structures of UO₂(tBu,MeO–saldien–X) showed that the U–X bond strength follows U–O ≈ U–NH > U–S. Conditional stability constants (β_X) of UO₂(tBu,MeO–saldien–X) in ethanol were investigated to understand the effect of X on thermodynamic stability. The log β_X decrease in the order of UO₂(tBu,MeO–saldien–NH) (log β_NH = 10) > UO₂(tBu,MeO–saldien–O) (log β_O = 7.24) > UO₂(tBu,MeO–saldien–S) (log β_S = 5.2). This trend cannot be explained only by Pearson's Hard and Soft Acids and Bases (HSAB) principle, but rather follows the order of basicity of X. Theoretical calculations of UO₂(tBu,MeO–saldien–X) suggested that the ionic character of U–X bonds decreases in the order of U–NH > U–O > U–S, while the covalency increases in the order U–O < U–NH < U–S. Redox potentials of all UO₂(tBu,MeO–saldien–X) in DMSO were similar to each other regardless of the difference in X. Spectroelectrochemical measurements and DFT calculations revealed that the center U⁶⁺ of each UO₂(tBu,MeO–saldien–X) undergoes one-electron reduction to afford the corresponding uranyl(V) complex. Consequently, the difference in X of UO₂(tBu,MeO–saldien–X) affects the coordination of tBu,MeO–saldien–X²⁻ with UO₂²⁺. However, the HSAB principle is not always prominent, but the Lewis basicity and balance between ionic and covalent characters of the U–X interactions are more relevant to determine the bond strengths.