Thermal and Photochemical Reduction and Functionalization Chemistry of the Uranyl Dication, [UVIO2]2+

Chem. Rev., 2019, DOI:10.1021/acs.chemrev.9b00048

Bradley E. Cowie, Jamie M. Purkis, Jonathan Austin, Jason B. Love*, Polly L. Arnold*

Chemrev2019

The uranyl ion, [UVIO2]2+, possesses rigorously trans, strongly covalent, and chemically robust U-oxo groups. However, through the use of anaerobic reaction techniques, both one- and two-electron reductive functionalization of the uranyl oxo groups has been discovered and developed. Prior to 2010, this unusual reactivity centered around the reductive silylation of the uranyl ion which entailed conversion of the oxo ligands into siloxy ligands and reductive metalation of the uranyl oxo with Group 1 and f-block metals. This review surveys the large number of new examples of reductive functionalization of the uranyl ion that have been reported since 2010, including reductive borylation and alumination, metalation with d– or f-block metals, and new examples of reductive silylation. Other examples of oxo-group functionalization of [UVIO2]2+ that do not involve reduction, mainly with Group 1 cations, are also covered, along with new advances in the photochemistry of the uranyl(VI) ion that involve the transient formation of formally uranyl(V) [UVO2]+ ion.

Published by Prof. Jason Love

Jason Love was awarded a BSc(Hons) in Applied Chemistry by Salford University in 1989 followed by a PhD in rhenium polyhydride chemistry in 1993, working with John Spencer. Following a series of postdoctoral positions with Geoff Cloke (Sussex), Michael Fryzuk (UBC), and Martin Schröder (Nottingham) looking at alkene polymerisation, dinitrogen fixation, and anion-binding receptor chemistry, respectively, he was awarded a lectureship and Royal Society URF (1999-2004) at Sussex in 1999. In 2001, he moved to Nottingham University and then to Edinburgh University as a Senior Lecturer in 2007 and Reader in 2010, and is now Professor of Molecular Inorganic Chemistry (2015). He is the Edinburgh PI of the EPSRC CDT in Critical Resource Catalysis (CRITICAT) with St Andrews and Heriot-Watt Universities . He has researched chemistry across the Periodic Table, focusing at present on small molecule redox catalysis in relation to energy and resource sustainability, ligand design strategies for d- and f-element chemistry, supramolecular catalysis, and metal extraction and recycling processes.

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