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Issue 35, 2017
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Benzoquinonoid-bridged dinuclear actinide complexes

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We report the coordination chemistry of the tripodal tris[2-amido(2-pyridyl)ethyl]amine ligand, L, with thorium(IV) and uranium(IV). Using a salt-metathesis strategy from the potassium salt of this ligand, K3L, new actinide complexes were isolated, namely the dimeric thorium complex [ThCl(L)]2 (1) and the monomeric uranium complex UI(THF)(L) (2); under different crystallisation conditions, the dimeric uranium complex is also isolated, [UI(L)]2 (2-dimer). With the aim of studying electronic phenomena such as magnetic exchange between two actinide ions, we have synthesised the first examples of dinuclear, quinoid-bridged actinide complexes from dianionic 2,5-bis[2,6-(diisopropyl)anilide]-1,4-benzoquinone (QDipp) and 2,5-bis[2-(methoxy)anilide]-1,4-benzoquinone (QOMe) ligands. The resulting complexes are [Th(L)]2QDipp (3), [Th(THF)(L)]2QOMe (5) and [U(L)]2QOMe (6). The targeted [U(L)]2QDipp complex (4) could not be isolated. All isolated complexes have been characterised by spectroscopic methods and X-ray crystallography. The uranium(IV) complexes 2-dimer and 6 have been studied by SQUID magnetometry but indicate that there is negligible magnetic exchange between the two uranium(IV) ions. The reduced form of 6, [K(18-c-6)][6] is unstable and highly sensitive, but X-ray crystallography indicates that it is a novel UIVUIV complex bridged by a quinoid-radical.

Graphical abstract: Benzoquinonoid-bridged dinuclear actinide complexes

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The article was received on 26 Jul 2017, accepted on 14 Aug 2017 and first published on 23 Aug 2017

Article type: Paper
DOI: 10.1039/C7DT02728A
Dalton Trans., 2017,46, 11615-11625

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    Benzoquinonoid-bridged dinuclear actinide complexes

    S. Hohloch, J. R. Pankhurst, E. E. Jaekel, B. F. Parker, D. J. Lussier, M. E. Garner, C. H. Booth, J. B. Love and J. Arnold, Dalton Trans., 2017, 46, 11615
    DOI: 10.1039/C7DT02728A

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