Uranyl to Uranium(IV) Conversion through Manipulation of Axial and Equatorial Ligands

Abstract

The controlled manipulation of the axial oxo and equatorial halide ligands in the uranyl dipyrrin complex, UO₂Cl(L), allows the uranyl reduction potential to be shifted by 1.53 V into the range accessible to naturally occurring reductants that are present during uranium remediation and storage processes. Abstraction of the equatorial halide ligand to form the uranyl cation causes a 780 mV positive shift in the U^V/U^IV reduction potential. Borane functionalization of the axial oxo groups causes the spontaneous homolysis of the equatorial U-Cl bond and a further 750 mV shift of this potential. The combined effect of chloride loss and borane coordination to the oxo groups allows reduction of U^VI to U^IV by H₂ or other very mild reductants such as Cp*₂Fe. The reduction with H₂ is accompanied by a B-C bond cleavage process in the oxo-coordinated borane.