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Concomitant Carboxylate and Oxalate Formation From the Activation of CO2 by a Thorium(III) Complex.pdf (1.03 MB)

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

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posted on 2019-06-05, 08:52 authored by A Formanuik, F Ortu, CJ Inman, A Kerridge, L Castro, L Maron, DP Mills
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.

Funding

This work was supported by the EPSRC (grant numbers EP/L014416/1, EP/M023885/1 and EP/J002208/2), the Nuclear FiRST DTC and the University of Manchester. L.M. thanks the Humboldt Foundation and the Chinese Academy of Sciences for experienced researcher grants as well as CalMip for computing time. The authors thank Prof. F. G. N. Cloke and Dr N. Tsoureas (University of Sussex) for helpful discussions, advice and access to equipment for mechanistic studies.

History

Citation

Chemistry, 2016, 22 (50), pp. 17976-17979

Author affiliation

/Organisation/COLLEGE OF SCIENCE AND ENGINEERING/Department of Chemistry

Version

  • VoR (Version of Record)

Published in

Chemistry

Publisher

Wiley for ChemPubSoc Europe, Asian Chemical Editorial Society (ACES)

eissn

1521-3765

Copyright date

2016

Available date

2019-06-05

Publisher version

https://onlinelibrary.wiley.com/doi/full/10.1002/chem.201604622

Notes

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.

Language

en

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