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  • Title: Actinide covalency measured by pulsed electron paramagnetic resonance spectroscopy.
    Author: Formanuik A, Ariciu AM, Ortu F, Beekmeyer R, Kerridge A, Tuna F, McInnes EJL, Mills DP.
    Journal: Nat Chem; 2017 Jun; 9(6):578-583. PubMed ID: 28537586.
    Abstract:
    Our knowledge of actinide chemical bonds lags far behind our understanding of the bonding regimes of any other series of elements. This is a major issue given the technological as well as fundamental importance of f-block elements. Some key chemical differences between actinides and lanthanides-and between different actinides-can be ascribed to minor differences in covalency, that is, the degree to which electrons are shared between the f-block element and coordinated ligands. Yet there are almost no direct measures of such covalency for actinides. Here we report the first pulsed electron paramagnetic resonance spectra of actinide compounds. We apply the hyperfine sublevel correlation technique to quantify the electron-spin density at ligand nuclei (via the weak hyperfine interactions) in molecular thorium(III) and uranium(III) species and therefore the extent of covalency. Such information will be important in developing our understanding of the chemical bonding, and therefore the reactivity, of actinides.
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