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

Formanuik, Alasdair and Ortu, Fabrizio and Inman, Christopher and Kerridge, Andrew and Castro, Ludovic and Maron, Laurent and Mills, David (2016) Concomitant Carboxylate and Oxalate Formation From the Activation of CO2 by a Thorium(III) Complex. Chemistry - A European Journal. ISSN 0947-6539

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Abstract

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.

Item Type:
Journal Article
Journal or Publication Title:
Chemistry - A European Journal
Uncontrolled Keywords:
/dk/atira/pure/subjectarea/asjc/1600
Subjects:
ID Code:
83075
Deposited By:
Deposited On:
25 Nov 2016 10:02
Refereed?:
Yes
Published?:
Published
Last Modified:
22 Nov 2020 04:30