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Concomitant Carboxylate and Oxalate Formation From the Activation of CO2 by a Thorium(III) Complex

Research output: Contribution to journalJournal articlepeer-review

E-pub ahead of print
  • Alasdair Formanuik
  • Fabrizio Ortu
  • Christopher Inman
  • Andrew Kerridge
  • Ludovic Castro
  • Laurent Maron
  • David Mills
<mark>Journal publication date</mark>27/10/2016
<mark>Journal</mark>Chemistry - A European Journal
Publication StatusE-pub ahead of print
Early online date27/10/16
<mark>Original language</mark>English


Improving our comprehension of diverse CO2 activation pathways is of vital importance for the widespread future utilization of this abundant greenhouse gas. CO2 activation by uranium(III) complexes is now relatively well understood, with oxo/carbonate formation predominating as CO2 is readily reduced to CO, but isolated thorium(III) CO2 activation is unprecedented. We show that the thorium(III) complex, [Th(Cp′′)3] (1, Cp′′={C5H3(SiMe3)2-1,3}), reacts with CO2 to give the mixed oxalate-carboxylate thorium(IV) complex [{Th(Cp′′)2[κ2-O2C{C5H3-3,3′-(SiMe3)2}]}2(μ-κ2:κ2-C2O4)] (3). The concomitant formation of oxalate and carboxylate is unique for CO2 activation, as in previous examples either reduction or insertion is favored to yield a single product. Therefore, thorium(III) CO2 activation can differ from better understood uranium(III) chemistry.