Synthesis and Structural Characterization of Hydrolysis Products within the Uranyl Iminodiacetate and Malate Systems

Abstract

The interplay of hydrolysis and chelation by organic ligands results in the formation of novel uranium species in aqueous solutions. Many of these molecular complexes have been identified by spectroscopic and potentiometric techniques, but a detailed structural understanding of these species is lacking. Identification of possible uranyl hydrolysis products in the presence of organic functional groups has been achieved by the crystallization of molecular species into a solid-state compound, followed by structural and chemical characterization of the material. The structures of three novel molecular complexes containing either iminodiacetate (<i>ida</i>) (Na₃[(UO₂)₃(OH)₃(ida)₃]·8H₂O (<b>1</b>)) or malate (<i>mal</i>) (K­(<i>pip</i>)₂[(UO₂)₃O­(<i>mal</i>)₃]·6H₂O (<b>2a</b>) (<i>pip</i> = C₄N₂H₁₂), (<b>2b</b>) (<i>pip</i>)₃[(UO₂)₃O­(<i>mal</i>)₃]·H₂O, and (<i>pip</i>)₆[(UO₂)₁₁(O)₄(OH)₄(<i>mal</i>)₆(CO₃)₂]·23H₂O (<b>3</b>)) ligands have been determined by single-crystal X-ray diffraction and have been chemically characterized by IR, Raman, and NMR spectroscopies. A major structural component in compounds <b>1</b> and <b>2</b> is a trimeric 3:3 uranyl <i>ida</i> or <i>mal</i> species, but different bridging groups between the metal centers create variations in the structural topologies of the molecular units. Compound <b>3</b> contains a large polynuclear cluster with 11 U atoms, which is composed of trimeric and pentameric building units chelated by <i>mal</i> ligands and linked through hydroxyl groups and carbonate anions. The characterized compounds represent novel structural topologies for U⁶⁺ hydrolysis products that may be important molecular species in near-neutral aqueous systems