Dataset Information

Nanosized Gadolinium and Uranium-Two Representatives of High-Reactivity Lanthanide and Actinide Metal Nanoparticles.

ABSTRACT: Gadolinium (Gd⁰) and uranium (U⁰) nanoparticles are prepared via lithium naphthalenide ([LiNaph])-driven reduction in tetrahydrofuran (THF) using GdCl₃ and UCl₄, respectively, as low-cost starting materials. The as-prepared Gd⁰ and U⁰ suspensions are colloidally stable and contain metal nanoparticles with diameters of 2.5 ± 0.7 nm (Gd⁰) and 2.0 ± 0.5 nm (U⁰). Whereas THF suspensions are chemically stable under inert conditions (Ar and vacuum), nanoparticulate powder samples show high reactivity in contact with, for example, oxygen, moisture, alcohols, or halogens. Such small and highly reactive Gd⁰ and U⁰ nanoparticles are first prepared via a dependable liquid-phase synthesis and stand as representatives for further nanosized lanthanides and actinides.

SUBMITTER: Schottle C

PROVIDER: S-EPMC6645660 | biostudies-literature | 2017 Dec

REPOSITORIES: biostudies-literature

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Nanosized Gadolinium and Uranium-Two Representatives of High-Reactivity Lanthanide and Actinide Metal Nanoparticles.

Schöttle Christian C Rudel Stefan S Popescu Radian R Gerthsen Dagmar D Kraus Florian F Feldmann Claus C

ACS omega 20171221 12

Gadolinium (Gd0) and uranium (U0) nanoparticles are prepared via lithium naphthalenide ([LiNaph])-driven reduction in tetrahydrofuran (THF) using GdCl3 and UCl4, respectively, as low-cost starting materials. The as-prepared Gd0 and U0 suspensions are colloidally stable and contain metal nanoparticles with diameters of 2.5 ± 0.7 nm (Gd0) and 2.0 ± 0.5 nm (U0). Whereas THF suspensions are chemically stable unde ...[more]

PMID: 31457432

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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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Dataset Information

Nanosized Gadolinium and Uranium-Two Representatives of High-Reactivity Lanthanide and Actinide Metal Nanoparticles.

Publications

Nanosized Gadolinium and Uranium-Two Representatives of High-Reactivity Lanthanide and Actinide Metal Nanoparticles.

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