Nitrilotripropionic Acid (ntp) and Other Polyamino Carboxylic-acids As Sequestering Agents for Beryllium(ii) - X-ray Crystal-structure of Sodium (nitrilotripropionato)beryllate(ii) Trihydrate, Na[be(ntp)]center-dot-3h(2)o

Chinea, E.;Dominguez, S.;Mederos, A.;Brito, F.;Germain, Gabriel;et.al.
(1995) Inorganic Chemistry — Vol. 34, n° 6, p. 1579-1587 (1995)

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  • Chinea, E.
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  • Dominguez, S.
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  • Mederos, A.
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  • Brito, F.
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  • Germain, GabrielUCLouvain
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Abstract
Potentiometric studies in aqueous solution at 25 degrees C and ionic strength 0.5 mol dm(-3) in NaClO4 show that beryllium(II) with different polyamino carboxylic acids forms the following complexes: EDTA (ethylenediaminetetraacetic), 1,2-PDTA(1,2-propylenediamine-N,N,N',N'-tetraacetic), and CDTA (trans-1,2-cyclohexanediamine-N,N,N',N'-tetraacetic) (ligands, H(4)L), [BeHL](-), [BeL](2-), and [Be-3(OH)(3)(HL)]; EDDADP (ethylenediamine-N,N'-diacetic-N,N'-dipropionic) and EDTP (ethylenediamine-N,N,N',N'-tetrapropionic) (ligands, H(4)L), [BeH(2)L], [BeHL](-), [BeL](2-), and [Be-3(OH)(3)(HL)]; o-PhDTA (o-phenylenediamine-N,N,N',N'-tetraacetic),3,4-TDTA (3,4-toluenediamine-N,N,N',N'-tetraacetic) and 4-Cl-o-PhDTA (4-chloro-o-phenylenediamine-N,N,N',N'-tetraacetic) (ligands, H(4)L), [BeHL](-) and [BeL](2-); NTA (nitrilotriacetic) (ligand H(3)L), [BeL](-) and [Be-3(OH)(3)(HL)](+); NDAP (nitrilodiaceticpropionic) (ligand H(3)L), [BeH(2)L](+), [BeHL], [BeL](-), [Be-3(OH)(3)(HL)](+), and [Be-3(OH)(3)L]; NADP (nitriloaceticdipropionic) (ligand, H(3)L), [BeHL] and [BeL](-); NTP (nitrilotripropionic) (ligand, H(3)L), [BeL](-). The following complexes are formed analogously for magnesium(II): o-PhDTA, 3,4-TDTA, and 4-Cl-o-PhDTA, [MgHL](-) and [MgL](2-); NADP and NTP, [MgHL] and [MgL](-). The stability constants were determined. From an aqueous solution of Be(OH)(2) and NTP (ratio 1:1), boiled until the Be(OH)(2) was completely dissolved, crystals of the complex sodium (nitrilotripropionato)beryllate(II) trihydrate, Na[Be(NC9H12O6)]. 3H(2)O were obtained. X-ray diffraction structural analysis revealed that, in the chelate complex [Be(NTP)](-) (hexagonal), P6(3), a = 11.4768(7) Angstrom, b = 11.4768(7) Angstrom, c = 6.2807(3) Angstrom, V = 716.44(7) Angstrom(3), Z = 2, R1 = 0.0433, wR2 = 0.1110), the tetrahedron BeNO3 is almost regular with a very slight distortion toward the symmetry C-3v, H-1, C-13, Be-9 NMR, IR spectra, and thermal analyses are studied. The selective uptake of beryllium(II), a very toxic cation, was analyzed by means of the chemical speciation diagrams as well as the so-called conditional or effective formation constants K-BeL(eff). With respect to H+, the order 3,4-TDTA greater than or equal to o-PhDTA > 4-Cl-o-PhDTA greater than or equal to NADP greater than or equal to NTP much greater than> NDAP > EDTA > EDTP > EDDADP is found for K-BeL(eff). This result indicates that, in competition with H+, o-PhDTA, 3,4-TDTA, 4-Cl-o-PhDTA, NADP, and NTP are good sequestering agents at pH 4.5-6 for beryllium(II), and analogously to o-PhDTA, these ligands can potentially be used for the analytical determination of beryllium(II). In the presence of Mg(2+)and H+ (Be2+ inhibits numerous enzymes that compete with Mg2+), the order NTP approximate to NADP much greater than o-PhDTA approximate to 3,4-TDTA > 4-Cl-o-PhDTA is found. In the presence of Mg2+, at pH 4-6, NTP and NADP practically only sequester Be2+! The advantages of NTP and NADP acids to sequester specifically beryllium(II) are evident. H-1, C-13, and Be-9 NMR studies confirm the potentiometric studies.
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Chinea, E., Dominguez, S., Mederos, A., Brito, F., Arrieta, JM., Sanchez, A., & Germain, G. (1995). Nitrilotripropionic Acid (ntp) and Other Polyamino Carboxylic-acids As Sequestering Agents for Beryllium(ii) - X-ray Crystal-structure of Sodium (nitrilotripropionato)beryllate(ii) Trihydrate, Na[be(ntp)]center-dot-3h(2)o. Inorganic Chemistry, 34(6), 1579-1587. https://doi.org/10.1021/ic00110a041 (Original work published 1995)