Uranium rhodium bonding in heterometallic complexes

Abstract

The heterotetra- and bimetallic uranium(IV)–rhodium(I) complexes [U^IVI₂(μ-OAr^P-1κ¹O,2κ¹P)₂Rh^I(μ-I)]₂ (2) (Ar^PO⁻ = 2-(diphenylphosphino)-6-tert-butyl-4-methylphenoxide) and U^IVI(μ-I)(μ-OAr^P-1κ¹O,2κ¹P)₃Rh^I (3) were prepared by treatment of U^IVI(OAr^P-κ²O,P)₃ (1) with rhodium(I) iodide olefin complexes. The reaction of 1 with the monodentate cyclooctene (coe) rhodium(I) precursor [(coe)₂Rh^II]₂ gives only the bimetallic complex [U^IVRh^I] 3, and with the diene [(cod)Rh^II]₂ (5) (cod = 1,5-cyclooctadiene), mixtures of [U^IVRh^I]₂ complex 2 and [U^IVRh^I] 3 along with (cod)Rh^IOAr^P-κ²O,P (4), a Rh^I 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 U^IV–Rh^I 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.