Oxidation of Calix[4] Pyrrole through a cis-Uranyl Intermediate

Uranyl (UO 2 2+ ), the most common nuclear waste product and a highly water soluble ion, has two strongly bound U=O bonds. These bonds exist, almost exclusively, as trans, or 180º from each other. By perturbing the oxo bonds from trans to the rare cis isomer (90º from each other), it is hypothesized to change the fragment’s solubility properties. In the event of a nuclear spill, changing these properties has the potential to aid in the separation of the highly soluble and toxic uranyl fragment from water. Perturbation of the 180º bond angle will be achieved by bonding a macrocyclic ligand, with Lewis base properties, to the uranyl fragment. Strong bases will be used to deprotonate secondary amines, in the calix [4] pyrrole and phthalocyanine ligands, to produce alkali metal ligand complexes. These alkali metal ligand complexes will be reacted with UO 2 Cl 2 THF 3 or UO 2 (OTF) 2 (THF) 3 , in a double displacement reaction, to potentially afford a bent uranyl complex. These complexes will be characterized using NMR (nuclear magnetic resonance) and x-ray crystallography.

Faculty Advisor: Yon Visell