title: Strongly coupled binuclear uranium-oxo complexes from uranyl oxo rearrangement and reductive silylation.
abstract: The most common motif in uranium chemistry is the d(0)f(0) uranyl ion [UO(2)](2+) in which the oxo groups are rigorously linear and inert. Alternative geometries, such as the cis-uranyl, have been identified theoretically and implicated in oxo-atom transfer reactions that are relevant to environmental speciation and nuclear waste remediation. Single electron reduction is now known to impart greater oxo-group reactivity, but with retention of the linear OUO motif, and reactions of the oxo groups to form new covalent bonds remain rare. Here, we describe the synthesis, structure, reactivity and magnetic properties of a binuclear uranium-oxo complex. Formed through a combination of reduction and oxo-silylation and migration from a trans to a cis position, the new butterfly-shaped Si-OUO(2)UO-Si molecule shows remarkably strong U(V)-U(V) coupling and chemical inertness, suggesting that this rearranged uranium oxo motif might exist for other actinide species in the environment, and have relevance to the aggregation of actinide oxide clusters.
authors.affiliation: EaStCHEM School of Chemistry, University of Edinburgh, Edinburgh EH9 3JJ, UK. polly.arnold@ed.ac.uk
authors.forename: Polly L
authors.initials: PL
authors.lastname: Arnold
authors.forename: Guy M
authors.initials: GM
authors.lastname: Jones
authors.forename: Samuel O
authors.initials: SO
authors.lastname: Odoh
authors.forename: Georg
authors.initials: G
authors.lastname: Schreckenbach
authors.forename: Nicola
authors.initials: N
authors.lastname: Magnani
authors.forename: Jason B
authors.initials: JB
authors.lastname: Love