Issue 17, 2017

Uranium rhodium bonding in heterometallic complexes


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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Article information

Article type
03 Dec 2016
25 Jan 2017
First published
03 Feb 2017
This article is Open Access
Creative Commons BY license

Dalton Trans., 2017,46, 5540-5545

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, 46, 5540 DOI: 10.1039/C6DT04570G

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