Rights statement: 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 https://onlinelibrary.wiley.com/doi/10.1002/chem.201605974 This article may be used for non-commercial purposes in accordance With Wiley Terms and Conditions for self-archiving.
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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 - Double Reduction of 4,4′-Bipyridine and Reductive Coupling of Pyridine by Two Thorium(III) Single-Electron Transfers
AU - Formanuik, Alasdair
AU - Ortu, Fabrizio
AU - Liu, Jingjing
AU - Lydia, Nodaraki
AU - Tuna, Floriana
AU - Kerridge, Andrew
AU - Mills, David
N1 - 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 https://onlinelibrary.wiley.com/doi/10.1002/chem.201605974 This article may be used for non-commercial purposes in accordance With Wiley Terms and Conditions for self-archiving.
PY - 2017/2/16
Y1 - 2017/2/16
N2 - 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.
AB - 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.
KW - electron transfer
KW - N ligands
KW - reduction
KW - subvalent compounds
KW - thorium
M3 - Journal article
VL - 23
SP - 2290
EP - 2293
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
SN - 0947-6539
IS - 10
ER -