Complexation of VIVin aqueous solution with glutaroimide–dioxime (H3L), a ligand proposed for the possible sequestration of uranium from seawater, was studied by the combined application of spectroscopic (EPR and UV/Vis), spectrometric (ESI-MS), electrochemical (CV), and computational (DFT) techniques. The results indicate that a rare non-oxido VIVspecies, with formula [VIVL2]2–, is formed in the pH range 3–5. It transforms into a usual VIVO complex, [VIVOL(OH)]2–, at pH > 6. The non-oxido species is characterized by a “type 3” EPR spectrum with Az≈ 126 × 10–4cm–1and a UV/Vis signal with ε > 2000 m–1cm–1in the visible region. The detection of VVspecies by ESI-MS spectrometry was related to two possible oxidation processes, the first one in solution and the second one in-source during the recording of the spectra. The cyclic voltammogram of [VIVL2]2–shows two quasi-reversible processes, at E1/2= –0.75 V and E1/2= 0.03 V, assigned to the VIV/VIIIreduction and VIV/VVoxidation, respectively. All the experimental results were verified by DFT calculations, which indicated that the geometry of the non-oxido VIVcomplex is intermediate between an octahedron and a trigonal prism and allowed us to predict its51V hyperfine coupling (HFC) tensor A, the electron absorption spectrum, the two redox processes in the cyclic voltammogram, and the electronic structure that, in turn, determines its EPR and UV/Vis behavior.
VIVO and VIVSpecies Formed in Aqueous Solution by the Tridentate Glutaroimide–Dioxime Ligand – An Instrumental and Computational Characterization / Sanna, Daniele; Ugone, Valeria; Sciortino, Giuseppe; Parker, Bernard F.; Zhang, Zhicheng; Leggett, Christina J.; Arnold, John; Rao, Linfeng; Garribba, Eugenio. - In: EUROPEAN JOURNAL OF INORGANIC CHEMISTRY. - ISSN 1434-1948. - 2018:17(2018), pp. 1805-1816. [10.1002/ejic.201800090]
VIVO and VIVSpecies Formed in Aqueous Solution by the Tridentate Glutaroimide–Dioxime Ligand – An Instrumental and Computational Characterization
Ugone, Valeria;Garribba, Eugenio
2018-01-01
Abstract
Complexation of VIVin aqueous solution with glutaroimide–dioxime (H3L), a ligand proposed for the possible sequestration of uranium from seawater, was studied by the combined application of spectroscopic (EPR and UV/Vis), spectrometric (ESI-MS), electrochemical (CV), and computational (DFT) techniques. The results indicate that a rare non-oxido VIVspecies, with formula [VIVL2]2–, is formed in the pH range 3–5. It transforms into a usual VIVO complex, [VIVOL(OH)]2–, at pH > 6. The non-oxido species is characterized by a “type 3” EPR spectrum with Az≈ 126 × 10–4cm–1and a UV/Vis signal with ε > 2000 m–1cm–1in the visible region. The detection of VVspecies by ESI-MS spectrometry was related to two possible oxidation processes, the first one in solution and the second one in-source during the recording of the spectra. The cyclic voltammogram of [VIVL2]2–shows two quasi-reversible processes, at E1/2= –0.75 V and E1/2= 0.03 V, assigned to the VIV/VIIIreduction and VIV/VVoxidation, respectively. All the experimental results were verified by DFT calculations, which indicated that the geometry of the non-oxido VIVcomplex is intermediate between an octahedron and a trigonal prism and allowed us to predict its51V hyperfine coupling (HFC) tensor A, the electron absorption spectrum, the two redox processes in the cyclic voltammogram, and the electronic structure that, in turn, determines its EPR and UV/Vis behavior.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.