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

Nicola L. Bell, Brian Shaw, Polly L. Arnold, Jason B. Love

Research output: Contribution to journalArticlepeer-review

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 po-tential. The combined effect of chloride loss and borane co-ordination 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.
Original languageEnglish
JournalJournal of the American Chemical Society
Early online date18 Feb 2018
DOIs
Publication statusE-pub ahead of print - 18 Feb 2018

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