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Thermodynamic and Multinuclear NMR Study of Beryllium(II) Hydrolysis and Beryllium(II) Complex Formation with Oxalate, Malonate, and Succinate Anions in Aqueous Solution

✍ Scribed by Lucia Alderighi; Antonio Bianchi; Alfredo Mederos; Stefano Midollini; Agustin Rodriguez; Alberto Vacca


Publisher
John Wiley and Sons
Year
1998
Tongue
English
Weight
403 KB
Volume
1998
Category
Article
ISSN
1434-1948

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✦ Synopsis


Beryllium(II) hydrolysis / Beryllium(II) complexes / Carboxylate ligands / Thermodynamics of complex formation / 9 Be-NMR spectra

The hydrolysis of beryllium(II) and its complexation by [Be 3 (OH) 3 ] 3+ , [Be 5 (OH) 6 ] 4+ , [Be 6 (OH) 8 ] 4+ , and Be(OH) 2 .

Complex formation of beryllium(II) with the dicarboxylate oxalate, malonate, and succinate in 0.5 mol dm -3 NaClO 4 aqueous solution at 298 K has been studied by means of ligands is invariably promoted by favourable entropic contributions (∆S°Ͼ 0), while the enthalpic terms are always potentiometric (pH-metric), microcalorimetric, and multinuclear NMR-spectroscopic measurements. The unfavourable (∆H°Ͼ 0). Malonate forms by far the most stable complexes owing to a more favourable (less protonation properties of the three ligands have also been investigated by potentiometry and microcalorimetry under endothermic) enthalpic contribution. These data reflect the fitting of the "bites" of the ligands with the stereochemically the same experimental conditions. Thermodynamic results are consistent with a previously proposed chemical model for required tetrahedral coordination geometry about the metal ion, as well as the ligand preorganization. beryllium(II) hydrolysis, involving the species [Be 2 OH] 3+ ,