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 UV/UIV 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 UVI to UIV 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.