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  • 1
    ISSN: 1434-1948
    Keywords: Beryllium(II) hydrolysis ; Beryllium(II) complexes ; Carboxylate ligands ; Thermodynamics of complex formation ; 9Be-NMR spectra ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The hydrolysis of beryllium(II) and its complexation by oxalate, malonate, and succinate in 0.5 mol dm-3 NaClO4 aqueous solution at 298 K has been studied by means of potentiometric (pH-metric), microcalorimetric, and multinuclear NMR-spectroscopic measurements. The protonation properties of the three ligands have also been investigated by potentiometry and microcalorimetry under the same experimental conditions. Thermodynamic results are consistent with a previously proposed chemical model for beryllium(II) hydrolysis, involving the species [Be2OH]3+, [Be3(OH)3]3+, [Be5(OH)6]4+, [Be6(OH)8]4+, and Be(OH)2. Complex formation of beryllium(II) with the dicarboxylate ligands is invariably promoted by favourable entropic contributions (ΔS° 〉 0), while the enthalpic terms are always unfavourable (ΔH° 〉 0). Malonate forms by far the most stable complexes owing to a more favourable (less endothermic) enthalpic contribution. These data reflect the fitting of the “bites” of the ligands with the stereochemically required tetrahedral coordination geometry about the metal ion, as well as the ligand preorganization.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Following X-ray crystal structure studies, the products of the reaction between Cu(II) halides and tris(hydroxymethyl)methylamine (TRIS) can be formulated as [Cu(TRISH-1)(TRIS)]2X2 and [Cu(TRISH-1)X]4 (X = Cl, Br). TRISH-1 is the deprotonated ligand. Initial metal-ligand stoichiometric ratios of 1:2 and 1:1 are required to obtain the former and the latter species, respectively. Relevant crystal data for the dimeric compound with X = Br are: monoclinic, a = 11.39(2), b = 10.049(2), c = 12.149(2) Å, β = 95.83(2)°, space group P21/c, Z = 2. The tetramer with X = Cl crystallizes in teh triclinic space group P 1 with a 9.182(1), b = 9.120(2), c = 8.817(1) Å, α = 88.95(1), β = 87.01(1), γ = 84.13(1), Z = 1. In the dimer, two square planar Cu(II)-units are held together by two H-bonds of the type O—H … O, which involve the O-atoms coordinated to the metals. The formation of an eight-membered cycle containing two metal ons ensues. The tetramer contains two dinuclear units formed by two metal centers, square planar in first approximation, which share one edge; the arrangement is significantly puckered at this vector. One of these bridging O-atoms has μ3 character as it serves as a weak apical donor for a Cu-atom of another binuclear unit. Thus a step-like geometry of the central core is obtained. Both compounds have constant magnetic moments at least down to the liquid N2 temperature. In this respect, they differ from other complexes of Cu(II) having comparable geometries, but temperature-dependent magnetic moments.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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