17O Nuclear magnetic resonance and relaxation in some chlorine oxyfluorides

Virlet, J.; Tantot, G.

doi:10.1016/0009-2614(76)80514-3

Cited by 18 publications

(2 citation statements)

References 8 publications

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“…If chemical exchange is slow, the I70-NMR spectrum of a dilute aqueous solution containing a hexaaqua metal ion consists of two resonances: one large, intense peak due to the bulk H,O and a smaller peak due to the M(H,O);+ resonance. A natural-abundance 1 7 0 -~p e c t r~m of acidified Al(ClO,), consists of a narrow, intense signal due to the bulk H,O at 0 ppm, and a quadruplet at +289 ppm due to C10; [14]. The bound-H20 signal is invisible on this spectrum.…”

mentioning

confidence: 97%

Variable‐Temperature and Variable‐Pressure¹⁷O‐NMR Study of Water Exchange of Hexaaquaaluminium(III)

Hugi‐Cleary

Helm

Merbach

1985

Helvetica Chimica Acta

103

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The transverse relaxation rate of H 2 0 in AI(H20)F has been measured as a function of temperature (255 to 417 K) and pressure (up to 220 MPa) using the I70-NMR line-broadening technique, in the presence of Mn(I1) as a relaxation agent. At high temperatures the relaxation rate is governed by chemical exchange with bulk H,O, whereas at low temperatures quadrupolar relaxation is prevailing. Low-temperature fast-injection I70-NMR was used to extend the accessible kinetic domain. The samples studied contained A13+ ( mechanism. These results of H 2 0 exchange on Al(H,O)P are discussed together with the available complex-formation rate data and permit also the assignment of I, mechanisms to these latter reactions.

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confidence: 97%

Variable‐Temperature and Variable‐Pressure¹⁷O‐NMR Study of Water Exchange of Hexaaquaaluminium(III)

Hugi‐Cleary

Helm

Merbach

1985

Helvetica Chimica Acta

103

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“…From the known values of the coupling constants involving the 170 nucleus (27), it is expected that T~-' (~~' L~) >> I'J('~'L~-'~o)~. Under these conditions, an indirect coupling between 1 7 0 and 13'La cannot be directly observed since the multiplet caused by the coupling would be collapsed (28). However, this coupling can provide a relaxation mechanism to the 170 nucleus (scalar relaxation of the second kind), and its contribution to the 170 linewidth, (v1f2)J, is given by eq.…”

Section: Resultsmentioning

confidence: 99%

A ¹³⁹La and ¹⁷O nuclear magnetic resonance study of the nature of La(III) first coordination sphere in acetonitrile solutions of hydrated lanthanum nitrate

Chen¹,

Detellier²

1994

Can. J. Chem.

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ZHIGANG CHEN and CHRISTIAN DETELLIER. Can. J. Chem. 72, 1797 (1994). The nature of the first coordination sphere of the La(II1) cation in acetonitrile solutions of La(N03)3.6H20 was investigated by 139La and 170 NMR. All three nitrate anions are coordinated to La(II1). There is a competition between water and acetonitrile molecules for the occupancy of the La(II1) first coordination sphere. The ' 3 9~a and 1 7 0 NMR results, obtained for various concentrations of La(N03)3.6H20, were quantitatively interpreted through a chemical equilibrium model. It was shown that the presence of only two La(II1) species, (La(II1) (NO3-),)' and (La(II1) (N03-)3.H20), in rapid exchange in solution could account for all the NMR results. The variation of the 139La and 1 7 0 NMR parameters (chemical shifts and relaxation rates) with the concentration of La(N03)3.6H20 results from the population increase of the species (La(II1) (N03-)3.H20). The chemical exchange between free and coordinated water molecules is also fast on the 170 NMR time scale. The 170 NMR signal of water is considerably broadened when it coordinates to the La(II1) cation. This broadening was attributed to both direct and indirect interactions between the two quadrupolar nuclei I7O and 1 3 9~a .The direct interaction comes from an increase of the electric field gradient at the I7O nucleus when a water molecule coordinates to the La(II1) cation. The indirect interaction results from an 170-139La scalar coupling. The detailed analysis of the 170 NMR spectra also allowed the determination of the indirect coupling constant between coordinated 170H2 and '39La(III), I ' J ( '~~_ '~~L a)(: Lanthanide ions are increasingly used as spectroscopic probes in biochemical and biological systems (1, 2), and a more detailed knowledge of their coordination behavior in the presence of specific ligands in solutions is needed. However, many aspects of their coordination chemistry remain unclear. For example, the nature and the structure of the chemical species present in aqueous solutions of their salts are not yet fully understood (3-5).It is likely that ion pairs be formed in the solutions of the tripositive lanthanoid ions ("Ln3+": y3+, La3+-Lu3+), particularly in poorly coordinating solvents. Bunzli and co-workers (6, 7) have investigated the interactions between lanthanoid cations and the perchlorate anion in anhydrous acetonitrile solutions by FTIR spectroscopy. They found that inner sphere complexes of Ln3+ with C104-were formed in these systems (6, 7). The nature of the solutions of lanthanide chloride in methanol and methanol-water mixtures has been studied by several techniques, including X-ray diffraction (8, 9), NMR spectroscopy (8-1 l), ultrasonic absorption measurements (12), 'Author to whom correspondence may be addressed. Tel: (613) 564-2967, fax: (613) 564-6793, e-mail: DETSE@ACADVMl. UOTTAWA.CA.'Revision received April 7, 1994.and UV-Visible spectroscopy (13). On the basis of these studies, evidences were found that contact ion pairs are formed between Ln3+ and C1-in...

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17O-NMR-Spektroskopie zur Lösung chemischer Probleme

Klemperer

1978

Angew. Chem.

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Die NMR‐Spektroskopie des Isotops 17O, eines Quadrupolkerns mit geringer natürlicher Häufigkeit, wurde bisher wegen experimenteller Schwierigkeiten nur beschränkt zur Lösung chemischer Probleme herangezogen. Ein Vergleich der aus systematischen Studien strukturell verwandter Verbindungen erhaltenen Daten zeigt jedoch, daß nichtäquivalente Sauerstoffatome für gewöhnlich große Unterschiede in den chemischen Verschiebungen aufweisen und daß für 17O in spezifischen chemischen Umgebungen charakteristische Werte der chemischen Verschiebung beobachtet werden. Die gegenwärtige Verfügbarkeit von 17O‐angereichertem Material und von Fourier‐Transform‐NMR‐Geräten läßt für die nahe Zukunft eine ausgiebige Anwendung der 17O‐NMR‐Technik zur Lösung struktureller Probleme erwarten.

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17O Nuclear magnetic resonance and relaxation in some chlorine oxyfluorides

Cited by 18 publications

References 8 publications

Variable‐Temperature and Variable‐Pressure¹⁷O‐NMR Study of Water Exchange of Hexaaquaaluminium(III)

Variable‐Temperature and Variable‐Pressure¹⁷O‐NMR Study of Water Exchange of Hexaaquaaluminium(III)

A ¹³⁹La and ¹⁷O nuclear magnetic resonance study of the nature of La(III) first coordination sphere in acetonitrile solutions of hydrated lanthanum nitrate

17O-NMR-Spektroskopie zur Lösung chemischer Probleme

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17O Nuclear magnetic resonance and relaxation in some chlorine oxyfluorides

Cited by 18 publications

References 8 publications

Variable‐Temperature and Variable‐Pressure17O‐NMR Study of Water Exchange of Hexaaquaaluminium(III)

Variable‐Temperature and Variable‐Pressure17O‐NMR Study of Water Exchange of Hexaaquaaluminium(III)

A 139La and 17O nuclear magnetic resonance study of the nature of La(III) first coordination sphere in acetonitrile solutions of hydrated lanthanum nitrate

17O-NMR-Spektroskopie zur Lösung chemischer Probleme

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Variable‐Temperature and Variable‐Pressure¹⁷O‐NMR Study of Water Exchange of Hexaaquaaluminium(III)

Variable‐Temperature and Variable‐Pressure¹⁷O‐NMR Study of Water Exchange of Hexaaquaaluminium(III)

A ¹³⁹La and ¹⁷O nuclear magnetic resonance study of the nature of La(III) first coordination sphere in acetonitrile solutions of hydrated lanthanum nitrate