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Uranium rhodium bonding in heterometallic complexes.

ABSTRACT: The heterotetra- and bimetallic uranium(iv)-rhodium(i) complexes [U^IVI₂(?-OAr^P-1?¹O,2?¹P)₂Rh^I(?-I)]₂ (2) (Ar^PO^- = 2-(diphenylphosphino)-6-tert-butyl-4-methylphenoxide) and U^IVI(?-I)(?-OAr^P-1?¹O,2?¹P)₃Rh^I (3) were prepared by treatment of U^IVI(OAr^P-?²O,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-?²O,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.

SUBMITTER: Hlina JA

PROVIDER: S-EPMC5436036 | biostudies-literature | 2017 May

REPOSITORIES: biostudies-literature

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Uranium rhodium bonding in heterometallic complexes.

Hlina J A JA Wells J A L JAL Pankhurst J R JR Love Jason B JB Arnold P L PL

Dalton transactions (Cambridge, England : 2003) 20170501 17

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(OArP-κ2O,P)3 (1) with rhodium(i) iodi ...[more]

PMID: 28154865

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Project description:Heterobimetallic complexes containing short uranium-group 10 metal bonds have been prepared from monometallic IU(IV)(OAr(P)-?(2)O,P)3 (2) {[Ar(P)O](-) = 2-tert-butyl-4-methyl-6-(diphenylphosphino)phenolate}. The U-M bond in IU(IV)(?-OAr(P)-1?(1)O,2?(1)P)3M(0), M = Ni (3-Ni), Pd (3-Pd), and Pt (3-Pt), has been investigated by experimental and DFT computational methods. Comparisons of 3-Ni with two further U-Ni complexes XU(IV)(?-OAr(P)-1?(1)O,2?(1)P)3Ni(0), X = Me3SiO (4) and F (5), was also possible via iodide substitution. All complexes were characterized by variable-temperature NMR spectroscopy, electrochemistry, and single crystal X-ray diffraction. The U-M bonds are significantly shorter than any other crystallographically characterized d-f-block bimetallic, even though the ligand flexes to allow a variable U-M separation. Excellent agreement is found between the experimental and computed structures for 3-Ni and 3-Pd. Natural population analysis and natural localized molecular orbital (NLMO) compositions indicate that U employs both 5f and 6d orbitals in covalent bonding to a significant extent. Quantum theory of atoms-in-molecules analysis reveals U-M bond critical point properties typical of metallic bonding and a larger delocalization index (bond order) for the less polar U-Ni bond than U-Pd. Electrochemical studies agree with the computational analyses and the X-ray structural data for the U-X adducts 3-Ni, 4, and 5. The data show a trend in uranium-metal bond strength that decreases from 3-Ni down to 3-Pt and suggest that exchanging the iodide for a fluoride strengthens the metal-metal bond. Despite short U-TM (transition metal) distances, four other computational approaches also suggest low U-TM bond orders, reflecting highly transition metal localized valence NLMOs. These are more so for 3-Pd than 3-Ni, consistent with slightly larger U-TM bond orders in the latter. Computational studies of the model systems (PH3)3MU(OH)3I (M = Ni, Pd) reveal longer and weaker unsupported U-TM bonds vs 3.

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Uranium rhodium bonding in heterometallic complexes.

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Uranium rhodium bonding in heterometallic complexes.

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