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Research output: Contribution to Journal/Magazine › Journal article › peer-review
Research output: Contribution to Journal/Magazine › Journal article › peer-review
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TY - JOUR
T1 - Concomitant Carboxylate and Oxalate Formation From the Activation of CO2 by a Thorium(III) Complex
AU - Formanuik, Alasdair
AU - Ortu, Fabrizio
AU - Inman, Christopher
AU - Kerridge, Andrew
AU - Castro, Ludovic
AU - Maron, Laurent
AU - Mills, David
PY - 2016/10/27
Y1 - 2016/10/27
N2 - 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.
AB - 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.
M3 - Journal article
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
SN - 0947-6539
ER -