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

Research output: Contribution to journalArticle

  • External authors:
  • Alasdair Formanuik
  • Fabrizio Ortu
  • Christopher J. Inman
  • Andrew Kerridge
  • Ludovic Castro

Abstract

Improving our comprehension of diverse CO2 activation pathways is of vital importance for the widespread future utilization of an 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.

Bibliographical metadata

Original languageEnglish
Pages (from-to)17976-17979
Number of pages4
JournalChemistry: A European Journal
Volume22
Issue number50
Early online date27 Oct 2016
DOIs
StatePublished - 9 Dec 2016