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

Alasdair Formanuik; Fabrizio Ortu; Jingjing Liu; Lydia Nodaraki; Floriana Tuna; Andrew Kerridge; David Mills

doi:10.1002/chem.201605974

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

Alasdair Formanuik, Fabrizio Ortu, Jingjing Liu, Lydia Nodaraki, Floriana Tuna, Andrew Kerridge, David Mills

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Abstract

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.

Original language	English
Pages (from-to)	2290-2293
Number of pages	4
Journal	Chemistry: A European Journal
Volume	23
Issue number	10
Early online date	25 Jan 2017
DOIs	https://doi.org/10.1002/chem.201605974
Publication status	Published - 16 Feb 2017

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ThbipypyridineAAMAccepted author manuscript, 1.05 MB

CCDC 1496846: Experimental Crystal Structure Determination
Formanuik, A. (Contributor), Ortu, F. (Contributor), Liu, J. (Contributor), Nodaraki, L. (Contributor), Tuna, F. (Contributor), Kerridge, A. (Contributor) & Mills, D. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2017
DOI: 10.5517/ccdc.csd.cc1m7lct, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1m7lct&sid=DataCite
Dataset
CCDC 1496847: Experimental Crystal Structure Determination
Formanuik, A. (Contributor), Ortu, F. (Contributor), Liu, J. (Contributor), Nodaraki, L. (Contributor), Tuna, F. (Contributor), Kerridge, A. (Contributor) & Mills, D. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2017
DOI: 10.5517/ccdc.csd.cc1m7ldv, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1m7ldv&sid=DataCite
Dataset
CCDC 1519027: Experimental Crystal Structure Determination
Formanuik, A. (Contributor), Ortu, F. (Contributor), Liu, J. (Contributor), Nodaraki, L. (Contributor), Tuna, F. (Contributor), Kerridge, A. (Contributor) & Mills, D. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2017
DOI: 10.5517/ccdc.csd.cc1mznw4, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1mznw4&sid=DataCite
Dataset

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@article{10b18bbfadb3482db75774950507557c,

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

abstract = "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.",

author = "Alasdair Formanuik and Fabrizio Ortu and Jingjing Liu and Lydia Nodaraki and Floriana Tuna and Andrew Kerridge and David Mills",

year = "2017",

month = feb,

day = "16",

doi = "10.1002/chem.201605974",

language = "English",

volume = "23",

pages = "2290--2293",

journal = "Chemistry: A European Journal ",

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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 - Nodaraki, Lydia

AU - Tuna, Floriana

AU - Kerridge, Andrew

AU - Mills, David

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.

U2 - 10.1002/chem.201605974

DO - 10.1002/chem.201605974

M3 - Article

VL - 23

SP - 2290

EP - 2293

JO - Chemistry: A European Journal

JF - Chemistry: A European Journal

SN - 0947-6539

IS - 10

ER -

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

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Datasets

CCDC 1496846: Experimental Crystal Structure Determination

CCDC 1496847: Experimental Crystal Structure Determination

CCDC 1519027: Experimental Crystal Structure Determination

Cite this