Nuclear Magnetic Resonance Studies of Ions in Pure and Mixed Solvents

Hinton, James F.; Amis, Edward S.

doi:10.1021/cr60248a002

Cited by 118 publications

(42 citation statements)

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“…There has been renewed interest in the solvation of simple anions, such as the halides, with protic solvents [1][2][3][4][5][6][7][8][9][10]. The strength of alcoholhalide interactions have been shown by IR spectroscopy [1,2] to depend upon the anion in the order F-> Cl-> Br->I-, as was also observed by NMR methods [3].…”

Section: Lbl-1630mentioning

confidence: 99%

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Hydration of the halide ions in certain organic solvents

Kenjo¹,

Diamond²

1974

Journal of Inorganic and Nuclear Chemistry

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LBL-1630The amount of water co-extracted by the halide anions into several solvents has been determined. The order was always Gl-> Br-> I-, and at high organic..;.phase salt concentrations, the hydration numbers increased with increasing concentration, apparently paralleling the formation of ion pairs and higher ion aggregates. In nitrobenzene· the lower, limiting values are 3. 3, 1. 8, and 1. 0 moles of water per anion for Cl-, Br-, and I~, respectively.With dichloroethane as solvent, and more particularly with chloroform, solvation of the anion by the (weakly) acid proton of the diluent replaces part of the hydration, and the hydration number observed decreases markedly. For a number of reasons, the hydration numbers observed are lower limits to the first-shell hydration or coordination number of the anion.

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Section: Lbl-1630mentioning

confidence: 99%

“…A study of UV and IR spectra suggested that the solvation number of the tetrahexylammonium iodide-alcohol complex was unity [6]. The hydration numbers of the halides as determined in aqueous solution by NMR methods [7,8] are 1.6 for F-, 0-2 for Cl-, and 1 for. Br-.…”

Section: Lbl-1630mentioning

confidence: 99%

Hydration of the halide ions in certain organic solvents

Kenjo¹,

Diamond²

1974

Journal of Inorganic and Nuclear Chemistry

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“…Evaluation of a,, is of considerable importance, since the electrostatic contribution to the chemical shift is needed in studies of ionic hydration (20). In the past, a,, has been estimated (21) or assumed to be equal to a,,; it appears that this may have led to an underestimate of the polarization contribution to hydration shifts.…”

Section: Chen7ical Shqt In the Complexmentioning

confidence: 99%

Anion–molecule complexes in solution. III. Nuclear magnetic resonance studies of halide ion–alcohol association

Green¹,

Martin²,

Cassie³

et al. 1969

Can. J. Chem.

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Certain alkyl-, aryl-, and arene-substituted alcohols form linear, hydrogen bonded complexes with bromide and other halide ions in tetrachloromethane. The hydroxyl proton shifts ca. 4 p.p.m. downfield in the complex, regardless of the degree or type of substitution. The interaction is enhanced by inductive electron withdrawal by substituents on the C-0-H moiety. A comparison of the present results with infrared spectroscopy shows that the absorption at ca. 3300 cm-I is entirely due to 1 :I alcohol-anion complexes. The a coefficient in Buckingham's equation for electrostatic interaction of a molecule with an ion, 8csE = aE, -bE2, is found to be 5.5 for alcohol 0-H bonds.Canadian Journal of Chemistry, 47, 1639 (1969) Nuclear magnetic resonance (n.m.r.) and infrared (i.r.) spectroscopy have been used extensively in the detection and characterization of the hydrogen bonding of alcohols and other hydroxyl bearing compounds to a variety of bases (1-3). Characteristically, hydrogen bond formation results in a decrease in shielding of the hydrogen nucleus. The extent of this deshielding has been regarded as a measure of hydrogen bond strength, in much the same way as have hydrogen bond shifts and intensities in the i.r. (1,3,4). Both the i.r. frequency shift and the n.m.r. shielding change have been correlated with the enthalpy of hydrogen bond formation (5).Pursuant to our studies of specific complexes to anions in weakly interacting solvents, we have observed deshielding of hydroxyl protons in methanol, pjimary, secondary, and tertiary alcohols, and a phenol, of magnitude up to 4.5 p.p.m., on addition of a tetrabutylammonium salt to a dilute solution of the alcohol in tetrachloromethane. We interpret the monotonic salt concentration dependence of the hydroxyl proton shifts as arising from specific hydrogen bonded interaction of the alcohols with the anions. alcohol to alcohol hydrogen bonding, and the proton shielding observed as a function of the halide ion concentration. Experimental MaterialsMetllartol This was Shawinigan reagent grade, and contained less than 0.2% water when received. This material was dried by storing over 4A molecular sieves (m.s.) for several days; tlie initial vigorous effervescence ceased after about 24 h. The tightly stoppered vial was kept in tlie dry-box. Samples containing nietlianol and tetrabutylammonium bromide decomposed slowly, the n.ni.r. spectrum showing a change after 1 day, but no observable change within 1 11 of sample preparation. All speclra were obtained within 1 11 of preparation of the sample. E t l~a~~o lThis was 98 %, as received, and showed no benzene in the n.m.r. and, at most, traces of water. This niaterial was distilled, and a center fraction totalling ca. 75% collected on n1.s. The fraction collected was refluxed over tlie m.s. for 1 11. The material was then redistilled with a center fraction totalling ca. 50% being collected on m.s. (boiling range 0.4 "C). The tightly-stoppered flask was immediately transferred to the dry-box, where the ethanol was placed in a ...

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“…Early reports described solution behavior of alkali metal salts in water (1)(2)(3)(4). These salts remained dissociated and solvated until salt concentrations approached 5 to 15 molal (1, 2).…”

Section: Introductionmentioning

confidence: 99%

Alkali metal salt solvation study in 1,1,3,3-tetramethylurea using nuclear magnetic resonance spectroscopy

Ciolino¹,

Barker²

1989

Can. J. Chem.

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Can. J. Chem. 67,2206 (1989. The solution behavior of a series of alkali metal tetraphenylborates, perchlorates, and iodides in 1,1,3,3-tetramethylurea (TMU) has been studied by proton nuclear magnetic resonance (NMR) spectroscopy. TMU has a simple proton NMR spectrum consisting of one singlet at 2.75 ppm. Alkali metal tetraphenylborates and perchlorates were observed to be dissociated in TMU. Sodium iodide, however, was observed to be associated in TMU. Present results are compared with those from other NMR investigations in TMU and related nonaqueous solvents.Key words: alkali metal salt solvation, tetramethylurea, nuclear magnetic resonance, solute-solvent interactions.LAURA ANN CIOLINO et BARBARA JANE BARKER. Can. J. Chem. 67,2206Chem. 67, (1989. Faisant appel ? i la rmn du 'H, on a CtudiC le comportement d'une sCrie de tktraphknylborates, de perchlorates et d'iodures de mCtaux alcalins en solution dans la 1,1,3,3-tCtramCthylurke (TMU). La TMU posstde un spectre rmn du 'H qui est simple et qui ne comporte qu'un singulet i 2,75 ppm. On a observC que, dans la TMU, les titraphknylborates et les perchlorates des mCtaux alcalins sont dissocits. Toutefois, on a observC que l'iodure de sodium est associt dans la TMU. On compare ces rksultats avec ceux obtenus au cours d'autres Ctudes par rmn tant dans la TMU que dans d'autres solvants apparentCs et non-aqueux.Mots clks : solvatation des sels de mCtaux alcalins, tCtramCthylurke, rtsonance magnCtique nuclCaire, interactions solutksolvant.[Traduit par la revue]

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Nuclear Magnetic Resonance Studies of Ions in Pure and Mixed Solvents

Cited by 118 publications

References 202 publications

Hydration of the halide ions in certain organic solvents

Hydration of the halide ions in certain organic solvents

Anion–molecule complexes in solution. III. Nuclear magnetic resonance studies of halide ion–alcohol association

Alkali metal salt solvation study in 1,1,3,3-tetramethylurea using nuclear magnetic resonance spectroscopy

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