Articles producció científica> Química Física i Inorgànica

Are U-U Bonds Inside Fullerenes Really Unwilling Bonds?

  • Identification data

    Identifier: imarina:9295095
  • Authors:

    Moreno-Vicente, A
    Roselló, Y
    Chen, N
    Echegoyen, L
    Dunk, PW
    Rodríguez-Fortea, A
    de Graaf, C
    Poblet, JM
    Journal Of The American Chemical Society
    10.1021/jacs.2c12346
    Journal Of The American Chemical Society. 145 (12): 6710-6718
  • Others:

    Author, as appears in the article.: Moreno-Vicente, A; Roselló, Y; Chen, N; Echegoyen, L; Dunk, PW; Rodríguez-Fortea, A; de Graaf, C; Poblet, JM
    Department: Química Física i Inorgànica
    URV's Author/s: De Graaf, Cornelis / Moreno Vicente, Antonio / Poblet Rius, Josep Maria / Rodríguez Fortea, Antonio / Rosello Marin, Yannick
    Keywords: Space Pseudopotentials Metal multiple bonds Electronic-structure Chemistry Atoms
    Abstract: Previous characterizations of diactinide endohedral metallofullerenes (EMFs) Th2@C80 and U2@C80 have shown that although the two Th3+ ions form a strong covalent bond within the carbon cage, the interaction between the U3+ ions is weaker and described as an "unwilling" bond. To evaluate the feasibility of covalent U-U bonds, which are neglected in classical actinide chemistry, we have first investigated the formation of smaller diuranium EMFs by laser ablation using mass spectrometric detection of dimetallic U2@C2n species with 2n >= 50. DFT, CASPT2 calculations, and MD simulations for several fullerenes of different sizes and symmetries showed that thanks to the formation of strong U(5f3)-U(5f3) triple bonds, two U3+ ions can be incarcerated inside the fullerene. The formation of U-U bonds competes with U-cage interactions that tend to separate the U ions, hindering the observation of short U-U distances in the crystalline structures of diuranium endofullerenes as in U2@C80. Smaller cages like C60 exhibit the two interactions, and a strong triple U-U bond with an effective bond order higher than 2 is observed. Although 5f-5f interactions are responsible for the covalent interactions at distances close to 2.5 angstrom, overlap between 7s6d orbitals is still detected above 4 angstrom. In general, metal ions within fullerenes should be regarded as templates in cage formation, not as statistically confined units that have little chance of being observed.
    Thematic Areas: Química Materiais Interdisciplinar General chemistry Farmacia Engenharias iv Engenharias iii Engenharias ii Colloid and surface chemistry Ciências biológicas ii Ciências biológicas i Ciências agrárias i Ciência de alimentos Chemistry, multidisciplinary Chemistry (miscellaneous) Chemistry (all) Chemistry Catalysis Biochemistry Astronomia / física
    licence for use: https://creativecommons.org/licenses/by/3.0/es/
    Author's mail: coen.degraaf@urv.cat yannick.rosello@estudiants.urv.cat josepmaria.poblet@urv.cat antonio.rodriguezf@urv.cat
    Author identifier: 0000-0001-8114-6658 0000-0002-4533-0623 0000-0001-5884-5629
    Record's date: 2024-07-20
    Papper version: info:eu-repo/semantics/publishedVersion
    Link to the original source: https://pubs.acs.org/doi/10.1021/jacs.2c12346
    Licence document URL: http://repositori.urv.cat/ca/proteccio-de-dades/
    Papper original source: Journal Of The American Chemical Society. 145 (12): 6710-6718
    APA: Moreno-Vicente, A; Roselló, Y; Chen, N; Echegoyen, L; Dunk, PW; Rodríguez-Fortea, A; de Graaf, C; Poblet, JM (2023). Are U-U Bonds Inside Fullerenes Really Unwilling Bonds?. Journal Of The American Chemical Society, 145(12), 6710-6718. DOI: 10.1021/jacs.2c12346
    Article's DOI: 10.1021/jacs.2c12346
    Entity: Universitat Rovira i Virgili
    Journal publication year: 2023
    Publication Type: Journal Publications
  • Keywords:

    Biochemistry,Catalysis,Chemistry,Chemistry (Miscellaneous),Chemistry, Multidisciplinary,Colloid and Surface Chemistry
    Space
    Pseudopotentials
    Metal multiple bonds
    Electronic-structure
    Chemistry
    Atoms
    Química
    Materiais
    Interdisciplinar
    General chemistry
    Farmacia
    Engenharias iv
    Engenharias iii
    Engenharias ii
    Colloid and surface chemistry
    Ciências biológicas ii
    Ciências biológicas i
    Ciências agrárias i
    Ciência de alimentos
    Chemistry, multidisciplinary
    Chemistry (miscellaneous)
    Chemistry (all)
    Chemistry
    Catalysis
    Biochemistry
    Astronomia / física
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