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Issue 17, 2017
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Uranium rhodium bonding in heterometallic complexes

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Abstract

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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Supplementary files

Article information


Submitted
03 Dec 2016
Accepted
25 Jan 2017
First published
03 Feb 2017

This article is Open Access

Dalton Trans., 2017,46, 5540-5545
Article type
Paper

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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