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Comprehensive real space bonding analysis of tetravalent f-element complexes with Schiff-base ligands

Kloditz, R.; Radoske, T.; Patzschke, M.; Stumpf, T.


The contribution of the f-orbitals to chemical bonding leads to the rich chemistry of the actinides. This is in contrast to the lanthanides, where it is known that this contribution is less important. Of special interest is the influence of these orbitals on the bonding character of actinides and lanthanides with organic ligands reflecting natural binding motifs.
This study compares the different bonding behavior of tetravalent actinides and lanthanides with the Schiff base salen (see Fig. 1, left) by means of real-space bonding analysis. Our approach makes use of the quantum theory of atoms in molecules (QTAIM), plots of the non-covalent interactions (NCI) and density differences complemented by natural population analysis (NPA). Especially the local properties at the bond critical points (Fig. 1, right), for instance charge, density, ellipticity and others, can be used to characterize a bond’s order, strength, and covalent contribution. In addition, thermodynamic calculations on the stability of these complexes are presented since the difference in stability is a direct consequence of the different interaction strengths of the f elements.
First results reveal a strong interaction of the actinides, i.e. Th to Pu, with the oxygen of salen characterized by a high electron density concentration between the atoms. In contrast, the interaction between the actinides and the nitrogen of salen is much weaker. The delocalization index, density and Laplacian reveal a significant increase of covalency for Pa to Pu compared to Th and Ce being an indicator of the contribution of the f-electrons. Tetravalent Ce as a lanthanide analogue of Th is expected to show a similar bonding behavior, but, surprisingly, this is not the case for all investigated bonding properties.
Such a detailed analysis of the electronic properties of actinide compounds will help to improve understanding of their behavior in the environment as well as in technical processes and leads to the possibility to predict properties of unknown complexes.

Keywords: Actinides; Quantum chemistry; DFT; Bonding; Covalency

  • Lecture (Conference)
    Journees des Actinides, 14.-18.04.2019, Erice, Italien


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