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  • 1
    ISSN: 0022-2364
    Quelle: Elsevier Journal Backfiles on ScienceDirect 1907 - 2002
    Thema: Physik
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 2
    ISSN: 1572-8927
    Schlagwort(e): Nitrogen-15 ; NMR ; praseodymium-nitrate complexes ; water-acetone mixtures ; contact ion-pairing
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract A direct, low-temperature nitrogen-15(15N) NMR technique has been applied to the study of inner-shell complex formation between praseodymium(III) and nitrate ion in aqueous solvent mixtures. In water-acetone mixtures at −95°C, ligand exchange is slow enough to permit the observation of15N NMR signals for uncomplexed and coordinated nitrate ion, but satisfactory resolution is obtained only by the addition of Freon-12 to these systems for study at −110 to −115°C. Four coordinated nitrate signals are generally observed and a very small signal for an additional complex, or an isomer of one of the others, appears at the highest nitrate concentrations. Signals for the mono-and dinitrato complexes are unambiguously identified, but with the exception of the trinitrato complex, several possibilities exist for the remaining peaks. To overcome excessive viscosity signal broadening, measurements in methanol and ethanol are possible only with praseodymium trifluoromethanesulfonate (triflate). Coordinated nitrate signals in aqueous and anhydrous methanol are observed only for the mono-and dinitrato species, and signal areas indicate a maximum of two moles of nitrate per Pr(III) are complexed. A third signal is evident in the ethanol solution spectra, and the presence of this higher complex was confirmed by area measurement of the fraction of bound nitrate. The extent of complex formation in these solvent systems is attributed to differences in the dielectric constant. A comparison of the complexing tendencies of Pr(III) to other ions studied by this NMR method suggests the possibility of a coordination number change across the lanthanide series. Preliminary15N NMR results for metal-ion complexes with the isothiocyanate ion are presented.
    Materialart: Digitale Medien
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  • 3
    ISSN: 1572-8927
    Schlagwort(e): Carbon-13 ; nitrogen-15 ; NMR ; samarium-nitrate complexes ; samarium-isothiocyanate complexes
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The extent of inner-shell, contact ion-pairing between samarium(III)-nitrate and in a preliminary manner, samarium(III)-isothiocyanate, has been determined by a direct, low-temperature, multinuclear magnetic resonance technique. In water-acetone mixtures containing Freon-12 or Freon-22, the slow exchange condition is achieved at −110 to −120°C, permitting the observation of15N NMR resonance signals for bulk and coordinated nitrate. In these mixtures, signals are observed for Sm(NO3)2+, Sm(NO3) 2 + , and two higher complexes, possibly the tetranitrato with either the penta-or hexanitrato.1H NMR signals for bound water molecules in these mixtures were observed, but accurate hydration numbers can not yed be determined. In anhydrous or aqueous methanol mixtures,15N NMR signals for only three complexes are observed, with the dinitrato clearly dominating. Using15N and35Cl NMR chemical shift and linewidth measurements, the superior complexing ability of nitrate compared to perchlorate and chloride, was demonstrated. Successful preliminary13C and15N NMR measurements of Sm3+-NCS− interactions in water-acetone-Freon-22 mixtures also have been made. The13C NMR spectra reveal signals for five complexes, presumably Sm(NCS)2+ through Sm(NCS) 5 2− . In the15N NMR spectra, signals for only three complexes are observed (the result of insufficient spectral resolution.) displaced about +240 ppm from bulk anion.
    Materialart: Digitale Medien
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  • 4
    ISSN: 1572-8927
    Schlagwort(e): Hydrogen-1 ; nitrogen-15 ; chlorine-35 ; NMR ; erbium nitrate ; complexation ; acetone ; methanol
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The extent of inner-shell ion-pair formation of Er3+ with nitrate ion in aqueous mixtures has been studied by nitrogen-15 (15N) NMR spectroscopy. At low temperature, exchange is slow enough to permit the direct observation of15N signals for nitrate ions in the Er3+ solvation shell and in bulk medium. In water-acetone mixtures,15N NMR signals for the mono-and bis complexes are observed at low nitrate to Er3+ mole ratios, but only the bis complex is evident at higher anion concentrations. No spectral evidence for the tris complex was seen at any nitrate concentration. In water-methanol-acetone mixtures, signals for the mono and bis complexes persist even at higher nitrate concentrations, indicating a reduced tendency to ion-pair with increasing dielectric constant. Preliminary15N NMR results are presented for the nitrate complexes of other paramagnetic lanthanide ions.
    Materialart: Digitale Medien
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  • 5
    ISSN: 1572-8927
    Schlagwort(e): Nitrogen-15 NMR ; neodymium-nitrate complexes ; aqueous solvent mixtures
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract A study of contact ion-pair formation between the neodymium (III) and nitrate ions in aqueous solvent mixtures has been carried out by a direct, low temperature, nitrogen-15 (15N) nuclear magnetic resonance (NMR) technique. At low temperatures, −90 to −120°C ligand exchange is slow enough to permit the observation of15N NMR signals for uncomplexed nitrate ion, and this anion in the primary solvation shell of Nd(III). In aqueous mixtures with inert acetone and Freon-12, resonance signals for Nd(NO3)2+, Nd(NO3) 2 1+ , and two higher complexes are observed. Signal areas indicate these additional species are possibly a combination of the tetra-, penta-, and hexanitrato complexes, but not the trinitrato. In water-methanol, a medium of higher dielectric constant, complexation is much less and signals only for the mono-and dinitrato complexes are observed. The effect of solvent on complexation is demonstrated more clearly by a series of measurements in water-methanol-acetone mixtures.
    Materialart: Digitale Medien
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  • 6
    ISSN: 1572-8927
    Schlagwort(e): Hydrogen-1 ; carbon-13 ; nitrogen-15 ; NMR ; magnesiumisothiocyanate complexes
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract A hydrogen-1, carbon-13, and nitrogen-15 NMR study of magnesium(II)-isothiocyanate complexation in aqueous mixtures has been completed. At temperatures low enough to slow proton and ligand exchange, separate1H,13C, and15N NMR signals are observed for coordinated and bulk water molecules and anions. The1H NMR spectra reveal signals for the hexahydrate and the mono-through triisothiocyanato complexes, as well as two small signals attributed to [Mg(H2O)5(OH)]1+ and [Mg(H2O)4(OH)(NCS)]. Accurate hydration numbers were obtained from signal area integrations at each NCS− concentration. In the15N NMR spectra, signals also were observed for the mono-through triisothiocyanato complexes, and a small signal believed to be due to [Mg(H2O)4(OH)(NCS)]. Coordination number contributions for NCS− were measured from these spectra and when combined with the hydration numbers they totalled essentially six at each anion concentration. Signals for [Mg(H2O)5(NCS)]1+ through [Mg(H2O)3(NCS)3]1− also were observed in the13C NMR spectra and the area evaluations were comparable to the15N NMR results. An analysis of the magnitude and sign of the coordinated NCS− chemical shifts identified the nitrogen atom as the anion binding site. All spectra indicated [Mg(H2O)5(NCS)]1+ and [Mg(H2O)4(NCS)2] were the dominat isothiocyanato complexes over the entire range of anion concentrations. The inability to detect evidence for complexes higher than the triisothiocyanato reflects the competitive binding ability of water molecules and perhaps the decreased electrostatic interaction between NCS− and negatively charged higher complexes.
    Materialart: Digitale Medien
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  • 7
    ISSN: 1572-8927
    Schlagwort(e): Hydrogen-1 ; carbon-13 ; nitrogen-15 ; NMR ; lutetium(III) ; isothiocyanate ; complexation
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract A direct, low-temperature hydrogen-1, carbon-13, and nitrogen-15 nuclear magnetic resonance study of lutetium(III)-isothiocyanate complex formation in aqueous solvent mixtures has been completed. At −100°C to −120°C in water-acetone-Freon mixtures, ligand exchange is slowed sufficiently to permit the observation of separate1H,13C, and15N NMR signals for coordinated and free water and isothiocyanate ions. In the13C and15N spectra of NCS−, resonance signals for five complexes are observed over the range of concentrations studied. The13C chemical shifts of complexed NCS− varied from −0.5 ppm to −3 ppm from that of free anion. For the same complexes, the15N chemical shifts from free anion were about −11 ppm to −15 ppm. The magnitude and sign of the15N chemical shifts identified the nitrogen atom as the binding site in NCS−. The concentration dependence of the13C and15N signal areas, and estimates of the fraction of anion bound at each NCS−:Lu3+ mole ratio, were consistent with the formation of [(H2O)5Lu(NCS)]2+ through [(H2O)Lu(NCS)5]2−. Although proton and/or ligand exchange and the resulting bulk-coordinated signal overlap prevented accurate hydration number measurements, a good qualitative correlation of the water1H NMR spectral results with those of13C and15N was possible.
    Materialart: Digitale Medien
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  • 8
    ISSN: 1572-8927
    Schlagwort(e): Carbon-13 ; nitrogen-15 ; chlorine-35 ; NMR ; samarium(III) ; isothiocyanate ; Sm3+ − NCS− complexes ; water–acetone–Freon ; water–methanol
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Multinuclear magnetic resonance studies of trivalent lanthanide inner-shell ion-pairing with nitrate and isothiocyanate are continuing. For NCS− solutions in water–acetone–Freon mixtures at low temperature, generally −100 to −125°C, ligand exchange is slow enough to permit the observation of 13C and 15N NMR signals for coordinated and free anions. For samariuni(III) solutions, four coordinated NCS−signals, displaced about +35 ppm and +250 ppm from free anion, are observed in the 13C and 15N NMR spectra, respectively. The 13C and 15N NMR data are complementary, showing a signal area concentration dependence and measured coordination numbers consistent with the formation of Sm(NCS)2+ through Sm(NCS) 4 1 . The coordination numbers reach a maximum of about three moles of NCS− per mole of Sm(III) with both nuclides, a result confirmed by spectral appearance showing the dominance of Sm(NCS)3 at the highest concentration studied. An analysis of the chemical shifts indicates that binding occurs at the nitrogen atom of NCS−. In water–methanol, due to the higher dielectric constant of such mixtures, coordination was less extensive. A competitive binding study with Ci− by 35Ci NMR demonstrated conclusively the superior coordinating ability of NCS−.
    Materialart: Digitale Medien
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  • 9
    ISSN: 1572-8927
    Schlagwort(e): Nitrogen-15 ; chlorine-35 ; NMR ; cerium nitrate ; complexation ; water acetone mixtures
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract A study of the complex formation which occurs between cerium(III) and nitrate ions in aqueous solvent mixtures has been carried out by a direct, low-temperature, nitrogen-15 (15N) NMR technique. At temperatures in the range of −95 to −110°C, ligand exchange is slow enough to permit the observation of separate15N NMR signals for bulk nitrate, and this anion in the cerium(III) principal coordination shell. In water-acetone-Freon-12 mixtures, the spectra reveal the nitrato complexes do not form consecutively. Rather, signals are observed for Ce(NO3)2+, Ce(NO3) 2 1+ , and only two other higher order complexes, even at very high NO 3 − to Ce(III) mole ratios. Signal area evaluations were used to identify the possible higher order complexes. At comparable salt concentrations in aqueous-methanol mixtures, only Ce(NO3)2+ and Ce(NO3) 2 1+ are formed, reflecting a decreased tendency for complexation in media of higher dielectric constant.
    Materialart: Digitale Medien
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  • 10
    ISSN: 1572-8927
    Schlagwort(e): Carbon-13 ; nitrogen-15 ; NMR ; europium-nitrate complexes ; europium-isothiocyanate complexes
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract A direct, low-temperature nuclear magnetic resonance spectroscopic study of europium(III)-nitrate contact ion-pairing has been completed, and preliminary results for europium(III)-isothiocyanate have been obtained. In water-acetone-Freon mixtures, at −110°C to −120°C, four15N NMR signals are observed for coordinated nitrate ion. Area evaluations of the signals and their concentration dependence indicate the formation of Eu(NO3)2+, Eu(NO3) 2 1+ , and two higher complexes, possibly the tetra-, with either the penta-or hexanitrato. This correlates well with similar15N NMR results obtained for Ce(III), Pr(III), Nd(III), and Sm(III). As a result of a higher dielectric constant, complex formation is significantly less in water-methanol mixtures, wheein only three complexes form with Eu(NO3) 2 1+ dominating at the highest anion concentrations. Competitive complexing experiments in water-methanol also were made by35Cl NMR chemical shift and linewidth measurements, as well as15N NMR. Initial experiments with the Eu3+-NCS− system show four coordinated anion signals, displaced from the bulk anion peak by about −250 ppm and −2,500 ppm in the13C and15N NMR spectra, respectively. Area evaluations are consistent with the presence of Eu(NCS)2+ through Eu(NCS) 4 1- in these solutions. A consideration of the chemical shifts identified the nitrogen atom as the site of binding in the NCS−. A discussion of these preliminary results, as well as those for several other metal-ions, will be presented.
    Materialart: Digitale Medien
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