Double Reduction of 4,4′-Bipyridine and Reductive Coupling of Pyridine by Two Thorium(III) Single-Electron Transfers

Formanuik, Alasdair and Ortu, Fabrizio and Liu, Jingjing and Lydia, Nodaraki and Tuna, Floriana and Kerridge, Andrew and Mills, David (2017) Double Reduction of 4,4′-Bipyridine and Reductive Coupling of Pyridine by Two Thorium(III) Single-Electron Transfers. Chemistry - A European Journal, 23 (10). pp. 2290-2293. ISSN 0947-6539

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The redox chemistry of uranium is burgeoning and uranium(III) complexes have been shown to promote many interesting synthetic transformations. However, their utility is limited by their reduction potentials, which are smaller than many non‐traditional lanthanide(II) complexes. Thorium(III) has a greater redox potential so it should present unprecedented opportunities for actinide reactivity but as with uranium(II) and thorium(II) chemistry, these have not yet been fully realized. Herein we present reactivity studies of two equivalents of [Th(Cp′′)3] (1, Cp′′={C5H3(SiMe3)2‐1,3}) with 4,4′‐bipyridine or two equivalents of pyridine to give [{Th(Cp′′)3}2{μ‐(NC5H4)2}] (2) and [{Th(Cp′′)3}2{μ‐(NC5H5)2}] (3), respectively. As relatively large reduction potentials are required to effect these transformations we have shown that thorium(III) can promote reactions that uranium(III) cannot, opening up promising new reductive chemistry for the actinides.

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Journal Article
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Chemistry - A European Journal
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This is the peer reviewed version of the following article:A. Formanuik, F. Ortu, J. Liu, L. E. Nodaraki, F. Tuna, A. Kerridge, D. P. Mills, Chem. Eur. J. 2017, 23, 2290. which has been published in final form at This article may be used for non-commercial purposes in accordance With Wiley Terms and Conditions for self-archiving.
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08 Aug 2018 15:42
Last Modified:
18 Sep 2023 01:24