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Synthesis, structure and redox properties of single-atom bridged diuranium complexes supported by aryloxides.

ABSTRACT: Single-atom (group 15 and group 16 anions) bridged dimetallic complexes of low oxidation state uranium provide a convenient route to implement multielectron transfer and promote magnetic communication in uranium chemistry, but remain extremely rare. Here we report the synthesis, redox and magnetic properties of N^3-, O^2-, and S^2- bridged diuranium complexes supported by bulky aryloxide ligands. The U(IV)/U(IV) nitride [Cs(THF)₈][(U(OAr)₃)₂(μ-N)], 1 could be prepared and characterized but could not be reduced. Reduction of the neutral U(IV)/U(IV) complexes [(U(OAr)₃)₂(μ-X)] A (X = O) and B (X = S) led to the isolation and characterization of the U(IV)/U(III) and U(III)/U(III) analogues. Complexes [(K(THF)₄)₂(U(OAr)₂)₂(μ-S)₂], 5 and [K(2.2.2-cryptand)]₂[(U(OAr)₃)₂(μ-S)], 6 are the first examples of U(III) sulphide bridged complexes. Computational studies and redox properties allow the reactivity of the dimetallic complexes to be related to their electronic structure.

SUBMITTER: Hsueh FC

PROVIDER: S-EPMC11320667 | biostudies-literature | 2024 Aug

REPOSITORIES: biostudies-literature

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Synthesis, structure and redox properties of single-atom bridged diuranium complexes supported by aryloxides.

Hsueh Fang-Che FC Barluzzi Luciano L Rajeshkumar Thayalan T Scopelliti Rosario R Zivkovic Ivica I Maron Laurent L Mazzanti Marinella M

Dalton transactions (Cambridge, England : 2003) 20240813 32

Single-atom (group 15 and group 16 anions) bridged dimetallic complexes of low oxidation state uranium provide a convenient route to implement multielectron transfer and promote magnetic communication in uranium chemistry, but remain extremely rare. Here we report the synthesis, redox and magnetic properties of N3-, O2-, and S2- bridged diuranium complexes supported by bulky aryloxide ligands. The U(IV)/U(IV) nitride [Cs(THF)8][(U(OAr)3)<sub ...[more]

PMID: 39051943

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Project description:A new monoiminoacenaphthenone 3,5-(CF3)2C6H3-mian (complex 2) was synthesized and further exploited, along with the already known monoiminoacenaphthenone dpp-mian, to obtain oxidovanadium(IV) complexes [VOCl2(dpp-mian)(CH3CN)] (3) and [VOCl(3,5-(CF3)2C6H3-bian)(H2O)][VOCl3(3,5-(CF3)2C6H3-bian)]·2.85DME (4) from [VOCl2(CH3CN)2(H2O)] (1) or [VCl3(THF)3]. The structure of all compounds was determined using X-ray structural analysis. The vanadium atom in these structures has an octahedral coordination environment. Complex 4 has an unexpected structure. Firstly, it contains 3,5-(CF3)2C6H3-bian instead of 3,5-(CF3)2C6H3-mian. Secondly, it has a binuclear structure, in contrast to 3, in which two oxovanadium parts are linked to each other through V=O···V interaction. This interaction is non-covalent in origin, according to DFT calculations. In structures 2 and 3, non-covalent π-π staking interactions between acenaphthene moieties of the neighboring molecules (distances are 3.36-3.40 Å) with an estimated energy of 3 kcal/mol were also found. The redox properties of the obtained compounds were studied using cyclic voltammetry in solution. In all cases, the reduction processes initiated by the redox-active nature of the mian or bian ligand were identified. The paramagnetic nature of complexes 3 and 4 has been proven by EPR spectroscopy. Complexes 3 and 4 exhibited high catalytic activity in the oxidation of alkanes and alcohols with peroxides. The yields of products of cyclohexane oxidation were 43% (complex 3) and 27% (complex 4). Based on the data regarding the study of regio- and bond-selectivity, it was concluded that hydroxyl radicals play the most crucial role in the reaction. The initial products in the reactions with alkanes are alkyl hydroperoxides, which are easily reduced to their corresponding alcohols by the action of triphenylphosphine (PPh3). According to the DFT calculations, the difference in the catalytic activity of 3 and 4 is most likely associated with a different mechanism for the generation of ●OH radicals. For complex 4 with electron-withdrawing CF3 substituents at the diimine ligand, an alternative mechanism, different from Fenton's and involving a redox-active ligand, is assumed.

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Synthesis, structure and redox properties of single-atom bridged diuranium complexes supported by aryloxides.

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Synthesis, structure and redox properties of single-atom bridged diuranium complexes supported by aryloxides.

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