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Uranium rhodium bonding in heterometallic complexes

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The heterotetra- and bimetallic uranium(IV)–rhodium(I) complexes [UIVI2(μ-OArP-1κ1O,2κ1P)2RhI(μ-I)]2 (2) (ArPO = 2-(diphenylphosphino)-6-tert-butyl-4-methylphenoxide) and UIVI(μ-I)(μ-OArP-1κ1O,2κ1P)3RhI (3) were prepared by treatment of UIVI(OArP2O,P)3 (1) with rhodium(I) iodide olefin complexes. The reaction of 1 with the monodentate cyclooctene (coe) rhodium(I) precursor [(coe)2RhII]2 gives only the bimetallic complex [UIVRhI] 3, and with the diene [(cod)RhII]2 (5) (cod = 1,5-cyclooctadiene), mixtures of [UIVRhI]2 complex 2 and [UIVRhI] 3 along with (cod)RhIOArP2O,P (4), a RhI side-product from the formation of 2. The complexes were characterised by single crystal X-ray diffraction, NMR and UV-vis-NIR spectroscopy, and electrochemistry. The UIV–RhI intermetallic distances in 2 (2.7601(5) Å) and 3 (2.7630(5) Å) are among the shortest between f-elements and transition metals reported to date. Despite almost identical U–Rh bond lengths in the solid state, in solution only weak, and very different interactions between the metal centres are found.

Graphical abstract: Uranium rhodium bonding in heterometallic complexes

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The article was received on 03 Dec 2016, accepted on 25 Jan 2017, published on 03 Feb 2017 and first published online on 03 Feb 2017

Article type: Paper
DOI: 10.1039/C6DT04570G
Citation: Dalton Trans., 2017, Advance Article
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    Uranium rhodium bonding in heterometallic complexes

    J. A. Hlina, J. A. L. Wells, J. R. Pankhurst, J. B. Love and P. L. Arnold, Dalton Trans., 2017, Advance Article , DOI: 10.1039/C6DT04570G

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