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The equilibrium constants for [NpO2·M]4+ (M = Al3+, In3+, Sc3+, Fe3+) in μ = 10 M nitric acid and [NpO2·Ga]4+ in μ = 10 M hydrochloric acid media have been… Click to show full abstract
The equilibrium constants for [NpO2·M]4+ (M = Al3+, In3+, Sc3+, Fe3+) in μ = 10 M nitric acid and [NpO2·Ga]4+ in μ = 10 M hydrochloric acid media have been determined. The trend in the interaction strength follows: Fe3+ > Sc3+ ≥ In3+ > Ga3+ ≫ Al3+. These equilibrium constants are compared to those of previously reported values for NpO2+ complexes with Cr3+ and Rh3+ within the literature. Thermodynamic parameters and bonding modes are discussed, with density functional theory and natural bond orbital analysis indicating that the NpO2+ dioxocation acts as a π-donor with transition-metal cations and a σ-donor with group 13 cations. The small changes in electron-donating ability is modulated by the overlap with the coordinating metal ion's valence atomic orbitals.
Journal Title: Inorganic chemistry
Year Published: 2017
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