Catalytic one-electron reduction of uranyl(VI) to Group 1 uranyl(V) complexes via Al(III) coordination
Markus Zegke1, Gary S Nichol, Polly L Arnold
1EaStCHEM School of Chemistry, The University of Edinburgh, David Brewster Road, Edinburgh EH9 3FJ, UK. Polly.Arnold@ed.ac.uk Jason.Love@ed.ac.uk.
Abstract:
Reactions between the uranyl(VI) Pacman complex [(UO2)(py)(H2L)] of the Schiff-base polypyrrolic macrocycle L and Tebbe's reagent or DIBAL result in the first selective reductive functionalisation of the uranyl oxo by Al to form [(py)(R2AlOUO)(py)(H2L)] (R = Me or (i)Bu). The clean displacement of the oxo-coordinated Al(III) by Group 1 cations has enabled the development of a one-pot, DIBAL-catalysed reduction of the U(VI) uranyl complexes to a series of new, mono-oxo alkali-metal-functionalised uranyl(V) complexes [(py)3(MOUO)(py)(H2L)] (M = Li, Na, K).
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