Quantitative UO bond activation in uranyl complexes via silyl radical transfer.

Reductive silylation of the uranyl dication with 1,4-bis(trimethylsilyl)dihydropyrazine, or "Mashima's reagent", is detailed. The reagent simultaneously delivers silylium ions and electrons to multiple uranyl complexes, i.e. a pyridine dipyrrolide uranyl complex and a common uranyl-containing starting material, UO 2 Cl 2 (OPPh 3 ) 2 . This reaction results in quantitative activation of thermodynamically robust UO bonds. The reductive functionalization of environmentally persistent actinyl species with Mashima's reagent is seen as a promising solution for nuclear waste remediation.