Controlled Deprotection and Reorganization of Uranyl Oxo Groups in a Binuclear Macrocyclic Environment

Abstract

Switching on uranium(V) reactivity: The silylated uranium(V) dioxo complex [(Me(3)SiOUO)(2)(L)(2)] (A) is inert to oxidation, but after two-electron reduction to [(Me(3)SiOUO)(2)(L)](2-) (1), it can be desilylated to form [OU(μ-O)(2)UO(L)(2)](2-) (2) with reinstated uranyl character. Removal of the silyl group uncovers new redox and oxo rearrangement chemistry for uranium, thus reforming the uranyl motif and involving the U(VI/V) couple in dioxygen reduction.