Abstract
A competitive solvation study of Al(ClO4)3, Ga(ClO4)3, In(ClO4)3, UO2(ClO4)2, and UO2(NO3)2 in water-acetone-dimethylsulfoxide (DMSO) and water-acetone-hexamethylphosphoramide (HMPT) mixtures has been carried out by direct H1 and P31 nuclear magnetic resonance (NMR) techniques. At low temperature, proton and ligand exchange are slow enough in these systems to permit the observation of signals for bulk and coordinated molecules of water and the organic bases (DMSO and HMPT). Both DMSO and HMPT compete effectively with water for coordination sites in the Al3+, Ga3+, and In3+ systems, with steric effects dominating the HMPT results. Both Al3+ and In3+ are able to bind a maximum of two to three HMPT molecules, for example. In contrast, UO2+ is solvated selectively by the organic molecules to the allowed maximum of 4 molecules per cation. H1 and P31 NMR spectral results support the formation of only the mono-, tri-, and tetra-HMPT solvation complexes.
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Fratiello, A., Vidulich, G.A., Cheng, C. et al. A direct hydrogen-1 and phosphorus-31 nuclear magnetic resonance cation solvation study of Al(ClO4)3, Ga(ClO4)3, In(ClO4)3, UO2(ClO4)2, and UO2(NO3)2 in water-acetone-dimethylsulfoxide and water-acetone-hexamethylphosphoramide mixtures. J Solution Chem 1, 433–444 (1972). https://doi.org/10.1007/BF00645606
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DOI: https://doi.org/10.1007/BF00645606