Catalytic one-electron reduction of uranyl(VI) to Group 1 uranyl(V) complexes via Al(III) coordination

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).