“…Since vanadium(V) ion does not exhibit any d-d transition in the visible spectrum, the color observed must be attributed to a strong oxygen to metal charge-transfer absorbance band in the ultraviolet [26,27] that extends into the visible range. This behavior was observed in our previous works about the vanadium(V) complexation by acetohydroxamic [11], b-alaninehydroxamic [13], glycinehydroxamic and a-aminohydroxamic acids [28]. In all these cases there is no consumption or release of protons, as observed now.…”
“…Comparing the values attributed to asp-b-ha and glu-c-ha with b-alaha [13] it becomes clear that the presence of the carboxylic group in asp-b-ha increases the acidity of both amino and hydroxamic acid group and decrease the acidity of the amino group of gluc-ha.…”
“…(1) was applied and the final set of mononuclear species and their formation constants that fit the potentiometric data reasonably well are shown in Table 1. This table also includes data of the vanadium (V)-b-alaninehydroxamic acid system [13].…”
Section: Potentiometric Titrationsmentioning
confidence: 99%
“…In previous papers, we have demonstrated how combined potentiometric, spectrophotometric and 51 V NMR methods allowed the identification of several species and determination of their formation constants in aqueous solution containing vanadium(V) and acetohydroxamic acid [11,12] and b-alaninehydroxamic acid [13]. In both systems, at least two vanadium-ligand 0020-1693/$ -see front matter Ó 2010 Elsevier B.V. All rights reserved.…”
“…Since vanadium(V) ion does not exhibit any d-d transition in the visible spectrum, the color observed must be attributed to a strong oxygen to metal charge-transfer absorbance band in the ultraviolet [26,27] that extends into the visible range. This behavior was observed in our previous works about the vanadium(V) complexation by acetohydroxamic [11], b-alaninehydroxamic [13], glycinehydroxamic and a-aminohydroxamic acids [28]. In all these cases there is no consumption or release of protons, as observed now.…”
“…Comparing the values attributed to asp-b-ha and glu-c-ha with b-alaha [13] it becomes clear that the presence of the carboxylic group in asp-b-ha increases the acidity of both amino and hydroxamic acid group and decrease the acidity of the amino group of gluc-ha.…”
“…(1) was applied and the final set of mononuclear species and their formation constants that fit the potentiometric data reasonably well are shown in Table 1. This table also includes data of the vanadium (V)-b-alaninehydroxamic acid system [13].…”
Section: Potentiometric Titrationsmentioning
confidence: 99%
“…In previous papers, we have demonstrated how combined potentiometric, spectrophotometric and 51 V NMR methods allowed the identification of several species and determination of their formation constants in aqueous solution containing vanadium(V) and acetohydroxamic acid [11,12] and b-alaninehydroxamic acid [13]. In both systems, at least two vanadium-ligand 0020-1693/$ -see front matter Ó 2010 Elsevier B.V. All rights reserved.…”
“…497,498 Speciation studies on alkylhydroxamic acid-vanadate complexes give log K f values on the order of 7-38 depending on the pH. 499,500 Cinnamoylhydroxamate was shown to form 1:1 and 1:2 complexes with V(V) at 1.8 M HCl in 2-methyl-4-pentanone; the stepwise formation constants were given and an octahedral coordination geometry was suggested. 501 The first structurally characterized V-hydroxamate complexes were the V(V)-complexes of benzohydroxamic acid (92), 502 the dihydroxamate N,N′-dihydroxy-N,N′-diisopropylheptanediamide, 502 and N-phenylbenzohydroxamic acid (93).…”
Section: V(v) and V(iv) Hydroxamate Complexesmentioning
Chemical speciation of Mn(II) in aqueous solution has been investigated by means of density functional methods. Different geometries and electronic states of all species arising from the Mn(II) hydrolysis have been calculated. The Gibbs free energy of the hydrolysis reaction and the respective equilibrium constants have been estimated and compared with the available experimental data. Polarizable continuum model (PCM-UAHF/6-31ϩG(d)) was used to estimate the solvation energy. The ionization potential of the predominant species are linearly dependent on the number of hydroxyls in their structure. The Mn(II)/Mn(III) oxidation potential estimate is in good agreement with the experimental value, about 0.2 V smaller. The estimated hydrolysis reaction energies are in good agreement with the experimental values with an error of about 3 kcal mol Ϫ1 (PBE/TZVP). The unique exception is the [Mn(OH) 3 ] Ϫ hydrolysis constant which is not in good agreement with the experimental value. This is attributed to inaccuracy of the presently available experimental value and the PCM solvation free energy estimate. The results shown in this work reinforce the importance of the chemical speciation in order to understand at a molecular level the mechanism of processes involving transition metal ions.
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