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. 2016 Dec 12;22(50):17976-17979.
doi: 10.1002/chem.201604622. Epub 2016 Oct 27.

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

Alasdair Formanuik  1 , Fabrizio Ortu  1 , Christopher J Inman  2 , Andrew Kerridge  3 , Ludovic Castro  4 , Laurent Maron  4 , David P Mills  1
Affiliations

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

Alasdair Formanuik et al. Chemistry. .

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''={C5 H3 (SiMe3 )2 -1,3}), reacts with CO2 to give the mixed oxalate-carboxylate thorium(IV) complex [{Th(Cp'')2 [κ2 -O2 C{C5 H3 -3,3'-(SiMe3 )2 }]}2 (μ-κ2 :κ2 -C2 O4 )] (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.

Keywords: actinides; reduction; small molecule activation; subvalent compounds; thorium.

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Figures

Scheme 1
Scheme 1
Synthesis of 2 and 3 from 1.
Figure 1
Figure 1
Molecular structure of a) 2 and b) 3.2C7H8 with selected atom labelling and displacement ellipsoids set to 30 % probability level. Hydrogen atoms, minor disorder components and lattice solvent omitted for clarity.
Figure 2
Figure 2
Computed enthalpy reaction profile for the formation of 3.
See this image and copyright information in PMC

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