Uranyl oxo reduction and functionalisation by elements from across the periodic table: English

Arnold, Polly L., Purkis, Jamie M., Caciuffo, R, Walter, O., Kaltsoyannis, N., Parsons, S, Cowie, B., Bell, N. L., Zegke, M., Dutkiewicz, M., Shaw, B. and Love, J. B. (2019) Uranyl oxo reduction and functionalisation by elements from across the periodic table: English. Spring 2019 National Meeting & Expo of the American Chemical Society, Orlando, FL, USA. 31 Mar - 04 Apr 2019.

Abstract

The most common motif in uranium chemistry is the linear d0f0 uranyl ion [UO2]2+. The strong, covalent U=O bonds render the oxo groups poorly Lewis basic and unreactive, and its salts persistent environmental contaminants. However, using anaerobic techniques we have been able to reduce, reorganise, and functionalise one or both oxo groups for the first time. Originally, the use of a Pacman shaped ligand to prevent other equatorial reactivity, and focus reactions to a single oxo group, enabled us to study and control single electron reduction and selective functionalisation of the oxo groups with elements from H to Np and Pu, and build polymetallic structures based on robust [UVO2]+, [UIV(OE)2]2+ and UV2O4 butterfly motifs. Now, we have been able to extend this uranyl(V) chemistry to systems that can tune the reduction potentials to those within reach of environmentally relevant reductants such as hydrogen, and to the simplest of systems, containing only halide ligands. Many of the complexes have interesting electronic structures and properties such as single molecule magnetism.

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Contributors

Author: Jamie M. Purkis

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