Strongly coupled binuclear uranium-oxo complexes from uranyl oxo rearrangement and reductive silylation

Polly L Arnold, Guy M Jones, Samuel O Odoh, Georg Schreckenbach, Nicola Magnani, Jason B Love

Research output: Contribution to journalArticlepeer-review


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.
Original languageEnglish
Pages (from-to)221-7
Number of pages7
JournalNature Chemistry
Issue number3
Early online date21 Feb 2012
Publication statusPublished - 2012


  • Inorganic chemistry
  • Organometallic chemistry
  • Synthesis


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