Uranyl oxo activation and functionalization by metal cation coordination

Polly L. Arnold (1) , Anne-Frédérique Pécharman (1) , Emmalina Hollis (1) , Ahmed Yahia (2, 3) , Laurent Maron (2, 3) , Simon J. Parsons (1) , Jason B. Love (1)

1 University of Edinburgh
2 LPCNO - Laboratoire de physique et chimie des nano-objets
3 ICSM - UMR 5257 - Institut de Chimie Séparative de Marcoule

The oxo groups in the uranyl ion [UO$_2$]$^{2+}$ , one of many oxo cations formed by metals from across the periodic table—are particularly inert, which explains the dominance of this ion in the laboratory and its persistence as an environmental contaminant. In contrast, transition metal oxo (M=O) compounds can be highly reactive and carry out difficult reactions such as the oxygenation of hydrocarbons. Here we show how the sequential addition of a lithium metal base to the uranyl ion constrained in a ‘Pacman’ environment results in lithium coordination to the U=O bonds and single-electron reduction. This reaction depends on the nature and stoichiometry of the lithium reagent and suggests that competing reduction and C–H bond activation reactions are occurring.

Keywords: bond-dissociation energies; reduction; complexes; uranium

Domains: Chemical Sciences

Polly L. Arnold, Anne-Frédérique Pécharman, Emmalina Hollis, Ahmed Yahia, Laurent Maron, et al.. Uranyl oxo activation and functionalization by metal cation coordination. Nature Chemistry, 2010, 2 (12), pp.1056-1061. ⟨10.1038/nchem.904⟩. ⟨cea-02060610⟩