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Title: Concomitant Carboxylate and Oxalate Formation From the Activation of CO2 by a Thorium(III) Complex.
Authors: Formanuik, A
Ortu, F
Inman, CJ
Kerridge, A
Castro, L
Maron, L
Mills, DP
First Published: 7-Oct-2016
Publisher: Wiley for ChemPubSoc Europe, Asian Chemical Editorial Society (ACES)
Citation: Chemistry, 2016, 22 (50), pp. 17976-17979
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.
DOI Link: 10.1002/chem.201604622
eISSN: 1521-3765
Version: Publisher Version
Status: Peer-reviewed
Type: Journal Article
Rights: Copyright © the authors, 2016. This is an open-access article distributed under the terms of the Creative Commons Attribution License (, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.
Description: Full synthetic details, characterization data and computational data for 2 and 3 is available in the Supporting Information. Additional research data supporting this publication are available from The University of Manchester eScholar repository at DOI: 10.15127/1.302780.
Appears in Collections:Published Articles, Dept. of Chemistry

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