Density Functional Theory Guided Investigation of Ligand‐Induced Neptunyl‐Neptunyl Interactions.

Autor: Augustine, Logan J., Pyrch, Mikaela Mary F., Kravchuk, Dmytro V., Williams, Jay M., Mason, Sara E., Forbes, Tori Z.
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Zdroj: European Journal of Inorganic Chemistry; 5/12/2023, Vol. 26 Issue 14, p1-11, 11p
Abstrakt: Actinyl‐actinyl interactions are particularly prevalent for the pentavalent neptunyl cation (Np(V)O2)+ where these interactions appear either as a T‐ or D‐shape (diamond‐shape). T‐shaped interactions have been previously identified in high concentration Np(V) solutions containing simple anions (NO3−, ClO4−, Cl−) whereas D‐shaped have only been isolated in the solid‐state in the presence of carboxylate ligands. In this study, Density Functional Theory (DFT) calculations were paired with Raman spectroscopy to evaluate the formation of D‐shaped interactions in the presence of aliphatic (R=H (formate), CH3 (acetate), CH2CH3 (propionate)) and aromatic (R=C6H5 (benzoate), C6H4OH (4‐hydroxybenzoate), C5H4N (isonicotinate)) carboxylate ligands. DFT studies indicate that the ΔG to form hydrated T‐ and D‐shaped forms are not spontaneous but become so with the addition of the carboxylate ligands. Raman spectra of the Np(V) carboxylate solutions contained vibrational modes associated with the D‐shaped interactions, but spectral changes observed over time indicate a dynamic system. Crystallization experiments from the Np(V) carboxylate systems confirmed the presence of D‐shaped dimers for the aromatic carboxylates, suggesting that the choice of the anion in solution favors actinyl‐actinyl interactions even at low concentrations (≤20 mM) of Np(V). [ABSTRACT FROM AUTHOR]
Databáze: Complementary Index
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