HYDROGEN BONDING IN THE AMINE HYDROHALIDES: II. THE INFRARED SPECTRUM FROM 4000 TO 2200 CM−1

1960 ◽  
Vol 38 (1) ◽  
pp. 34-44 ◽  
Author(s):  
C. Brissette ◽  
C. Sandorfy
Keyword(s):  
Hydrogen Bonding ◽  
Hydrogen Bonds ◽  
Infrared Spectrum ◽  
Infrared Spectra ◽  
Primary Amine ◽  
Lithium Fluoride ◽  
Aliphatic Amine ◽  
Combination Bands ◽  
Lower Frequencies ◽  
Amine Salts

The infrared spectra of a number of amine hydrohalides have been measured in the lithium fluoride region.Hydrogen bonding and the torsional oscillations of the [Formula: see text] groups influence these spectra characteristically. The [Formula: see text] stretching frequencies give broad or fairly broadbands. They are near 3000 cm−1 for aliphatic primary amine salts. The corresponding band lies at somewhat lower frequencies for secondary amine salts and much lower for tertiary ones. The aromatic amine hydrohalides exhibit these bands at lower frequencies than do the aliphatic amine salts of the same order. There is a shift to higher frequencies in the series hydrochloride, hydrobromide, hydriodide.All these spectra contain a number of sharper bands which may or may not coincide with the hydrogen-bonded stretching bands. These are combination bands involving mainly deformation vibrations, and they shift to lower frequencies, throughout the series hydrochloride, hydrobromide, hydriodide.The importance of electrical anharmonicity for the appearance of these bands is stressed.The hydrogen bonds in amine hydrohalides appear to be largely electrostatic in character.

HYDROGEN BONDING IN THE AMINE HYDROHALIDES: I. GENERAL ASPECTS

1958 ◽  
Vol 36 (8) ◽  
pp. 1181-1206 ◽  
Author(s):  
Bernadette Chenon ◽  
C. Sandorfy
Keyword(s):  
Hydrogen Bonding ◽  
Solid State ◽  
Aqueous Solutions ◽  
Aromatic Amine ◽  
Aliphatic Amine ◽  
Bathochromic Shift ◽  
Text Type ◽  
General Aspects ◽  
Combination Bands ◽  
Amine Salts

The infrared spectra of 17 amine hydrohalides have been measured in the solid state, in aqueous solutions, and in their conjugate amine. Their NH+ stretching and scissoring bands are discussed.The stretching bands of hydrogen-bonded aliphatic and aromatic amine hydrohalides fall into the same part of the spectrum. In the solid state, the hydrogen bonds are of type [Formula: see text] The aliphatic amine salts usually exhibit many sharp bands, while the aromatic amine salts have broad but composite bands. Tertiary amine salts show a hypsochromic shift in the order hydrochloride, hydrobromide, hydriodide; primary and secondary aliphatic amine salts show a slight bathochromic shift in the same order. Primary and secondary aromatic amine salts behave less regularly, although in most cases the shift is hypsochromic. These facts can be explained qualitatively by considering the charge distribution in the ionized amino groups and the contribution of electrostatic and delocalization effects to the energy of the hydrogen bonds.The anharmonicity of the potential surface which causes the appearance of strong combination bands may lead to the broadening of bands or to many sharp bands. There is no parallelism in this latter case between shift and broadening of the bands.The assignment of a strong band which appears in many cases near 2000 cm−1 is discussed.The above-mentioned characteristic band shifting is absent in the spectra of aqueous solutions and it is concluded that in this case hydrogen bonding is not of the [Formula: see text] but of the [Formula: see text] type.

HYDROGEN BONDING IN THE AMINE HYDROHALIDES: III. NEAR-INFRARED SPECTRA OF ALIPHATIC AMINE HYDROHALIDES

1960 ◽  
Vol 38 (10) ◽  
pp. 1901-1910 ◽  
Author(s):  
P. Sauvageau ◽  
C. Sandorfy
Keyword(s):  
Hydrogen Bonding ◽  
Secondary Amine ◽  
Infrared Spectra ◽  
Near Infrared ◽  
Potential Surface ◽  
Aliphatic Amine ◽  
Bending Vibrations ◽  
Near Infrared Spectra ◽  
Combination Bands

The first overtones of the [Formula: see text] stretching fundamentals are very weak and difficult to locate. Binary combinations between [Formula: see text] stretching and [Formula: see text] bending vibrations and also [Formula: see text] stretching–bending combinations fall into the 4600–4400 cm−1 area for primary and secondary amine hydrohalides and are much stronger. The intensity of these combination bands is not due to the anharnionicity of the potential surface but to the electrical anharmonicity of bending vibrations.

H2O, HDO, and CH3OH Infrared Spectra and Correlation with Solvent Basicity and Hydrogen Bonding

1971 ◽  
Vol 49 (6) ◽  
pp. 837-856 ◽  
Author(s):  
D. N. Glew ◽  
N. S. Rath
Keyword(s):  
Hydrogen Bonding ◽  
Hydrogen Bonds ◽  
Infrared Spectra ◽  
Dibasic Acid ◽  
Tertiary Amines ◽  
Type Symmetry ◽  
Solvent Basicity ◽  
Organic Amines ◽  
Lower Frequencies ◽  
Hydrogen Bonded

A study has been made of the infrared O—H bands for CH3OH, DOH, and H2O in solution and of their correlation with hydrogen bonding and solvent basicity. Infrared bands for the three fundamentals and the first bending overtone of H2O and for the O—H stretching fundamentals of DOH and CH3OH have been measured between 30 and −40 °C in a solvent range extending from weakly interacting fluorocarbons to strongly hydrogen-bonding organic amines. The O—H stretching bands for the weakly acidic solutes CH3OH, DOH, and H2O are mostly Lorentzian in shape and move to lower frequencies with higher extinctions in the more basic solvents. Many correlations are found between the stretching frequencies and band areas, and between the frequencies and solvent basicity. Monofunctional CH3OH is found to be a stronger acid and forms stronger hydrogen-bonds with a given base than do the doubly bonded DOH and HOH which show equal dibasic acid strengths.The wide, overlapped, fundamental stretching bands for H2O strongly hydrogen-bonded to the tertiary amines and for ice have been partially resolved and unequivocally assigned, showing that there is no cross-over of the ν 3 and ν1 bands despite the strong hydrogen-bonding.At higher temperatures in solvents containing both hydrophobic and strongly basic groups water was found with the lower Cs type symmetry, in which unbonded O—H groups gave sharp bands in the 3680–3650 cm−1 region in addition to the wide hydrogen-bonded bands at lower frequencies.

scholarly journals The infrared spectra of protic ionic liquids: performances of different computational models to predict hydrogen bonds and conformer evolution

2020 ◽  
Vol 22 (14) ◽  
pp. 7497-7506 ◽  
Author(s):  
O. Palumbo ◽  
A. Cimini ◽  
F. Trequattrini ◽  
J.-B. Brubach ◽  
P. Roy ◽  
...  
Keyword(s):  
Hydrogen Bonding ◽  
Ionic Liquids ◽  
Hydrogen Bonds ◽  
Dft Calculations ◽  
Infrared Spectra ◽  
Computational Models ◽  
Far Infrared ◽  
Protic Ionic Liquids ◽  
Far Infrared Spectra

DFT calculations with the ωB97-D functional reproduce hydrogen bonding features of the far-infrared spectra of diethylmethylammonium methanesulfonate and diethylmethylammonium trifluoromethanesulfonate.

The influence of hydrogen bonding on the character of N—H and C=O stretching modes in 2-thiopyrrole-1,2-dicarboximide

1984 ◽  
Vol 62 (9) ◽  
pp. 1845-1849 ◽  
Author(s):  
Shanker Ram
Keyword(s):  
Hydrogen Bonding ◽  
Transition Temperature ◽  
Solid State ◽  
Hydrogen Bonds ◽  
Spectral Data ◽  
Infrared Spectra ◽  
Cyclic Dimer ◽  
Dilute Solutions ◽  
Two Phases ◽  
Thermodynamical Functions

The infrared spectra (200–4000 cm−1) of 2-thiopyrrole-1,2-dicarboximide (TPH) in solid and solution forms have been measured as a function of temperature, and a direct correlation has been obtained between the two phases and the type and extent of hydrogen bonding. It is suggested that TPH exists as cyclic dimer in the solid state (below 310 K) and in dilute solutions by the formation of two equivalent hydrogen bonds. At the transition temperature, ~310 K, the cyclic dimer undergoes to the open-cyclic dimer and persists in this structure till 410 K. In addition, the thermodynamical functions ΔH0, and ΔS0 have been estimated using the spectral data in solution.

THE INTERACTION OF SILICON TETRAFLUORIDE WITH METHANOL

1963 ◽  
Vol 41 (6) ◽  
pp. 1477-1484 ◽  
Author(s):  
J. P. Guertin ◽  
M. Onyszchuk
Keyword(s):  
Hydrogen Bonding ◽  
Magnetic Resonance ◽  
Absorption Band ◽  
Hydrogen Bonds ◽  
Infrared Spectrum ◽  
Proton Magnetic Resonance ◽  
Methanol Solution ◽  
Silicon Tetrafluoride ◽  
Conductivity Measurements ◽  
Bond Stretching

Silicon tetrafluoride reacts with methanol in a 1:4 mole ratio, forming the complex SiF4.4CH3OH, which freezes to a glass at about −20° and is completely dissociated in the gaseous phase at 25°. Conductivity measurements show clearly that it is a very weak electrolyte in methanol solution. Its infrared spectrum does not contain an Si—O bond stretching absorption band. Proton magnetic resonance measurements provide strong evidence of hydrogen bonding between silicon tetrafluoride and methanol. These results indicate that the structure of the complex requires tetracovalent rather than hexacovalent silicon and strong hydrogen bonds between methanol and each of the four fluorine atoms.

The Infrared Spectrum of Ethylene Oxide Clathrate Hydrate between 360 and 20 cm−1, at 100 °K

1972 ◽  
Vol 50 (21) ◽  
pp. 3443-3449 ◽  
Author(s):  
J. E. Bertie ◽  
D. A. Othen
Keyword(s):  
Hydrogen Bonds ◽  
Infrared Spectrum ◽  
Ethylene Oxide ◽  
Infrared Spectra ◽  
Far Infrared ◽  
Empirical Correlation ◽  
Strong Absorption ◽  
Water Molecules ◽  
Oxide Hydrate ◽  
Infrared Frequencies

The infrared spectra of authenticated samples of ethylene oxide hydrate and deuterate at 100 °K have been measured between 360 and 20 cm−1. The spectra confirm that the water molecules are orientationally-disordered and reorient slowly compared to far-infrared frequencies. An empirical correlation is suggested between the frequencies of strong absorption and the number of non-equivalent hydrogen bonds, their length and distribution. The contribution to the spectrum by the ethylene oxide intermolecular vibrations is discussed.

Hydrogen bonding in organic compounds. II. Amine-cabonyl interactions

1958 ◽  
Vol 11 (4) ◽  
pp. 529 ◽  
Author(s):  
AN Hambly ◽  
J Bonnyman
Keyword(s):  
Hydrogen Bonding ◽  
Hydrogen Bonds ◽  
Organic Compounds ◽  
Aromatic Compounds ◽  
Primary Amine ◽  
Intermolecular Hydrogen Bonding ◽  
Amine Group ◽  
Methyl Anthranilate ◽  
Infra Red ◽  
Related Compounds

A comparison of the infra-red spectra of typical aromatic compounds, with a primary amine group adjacent to a carbonyl group, with the spectra of related compounds, shows that, in the former, weak hydrogen bonding occurs between the two groups. The strength of the bonds formed is in the order : 1-aminoanthraquinone > 2-amino-acetophenone > methyl anthranilate, and the changes in carbonyl frequency are comparable with those of the symmetric NH2 stretching frequency. Stronger hydrogen bonds are formed in corresponding ortho-acetamido compounds. A brief study of the NH2 stretching frequencies of o-nitroamines in dioxan solution shows that there is considerable interaction between solute and solvent but this cannot be definitely attributed to intermolecular hydrogen bonding.

The influence of pressure on the infrared spectra of hydrogen-bonded solids. VI. Ammonium salts

1978 ◽  
Vol 31 (1) ◽  
pp. 11 ◽  
Author(s):  
SD Hamann
Keyword(s):  
Hydrogen Bond ◽  
Hydrogen Bonds ◽  
Infrared Spectra ◽  
Ammonium Salts ◽  
Bond Strengths ◽  
As If ◽  
Lower Frequencies ◽  
Hydrogen Bonded

The infrared spectra of 33 polycrystalline ammonium salts have been measured at 25°C, at pressures up to 45 kbar. The N-H stretching and bending bands of the hydrogen-bonded NH4+ ions of most of the salts shift anomalously to higher and to lower frequencies, respectively, as the pressure is raised. In this sense, the salts behave as if they had very strong hydrogen bonds, instead of quite weak ones. ��� A fairly good correlation exists between the N-H stretching frequencies of salts with N+-H...O bonds and their hydrogen bond strengths as measured by the minimum N+...O distances in their crystals.

A SPECTROSCOPIC STUDY OF HYDROGEN BONDING IN PERFORMIC AND PERACETIC ACIDS

1952 ◽  
Vol 30 (11) ◽  
pp. 821-830 ◽  
Author(s):  
Paul A. Giguère ◽  
A. Weingartshofer Olmos
Keyword(s):  
Hydrogen Bonding ◽  
Hydrogen Bonds ◽  
Spectroscopic Study ◽  
Infrared Spectra ◽  
Peracetic Acid ◽  
The Other ◽  
Frequency Shifts ◽  
Vapor State ◽  
Nonpolar Solvents ◽  
Intramolecular Hydrogen

The infrared spectra of concentrated performic and peracetic acids were measured in the rock-salt region. The most significant features are theO—H stretching frequency at 3310–3350 cm−1 and the OH bending frequency at 1450 cm−1 which, for both peracids, remain essentially the same in the vapor state as in the liquid or in solution in nonpolar solvents. This is attributed to intramolecular hydrogen bonds resulting in particularly stable five-membered rings,[Formula: see text]Steric conditions in the percarboxylic group are favourable to such ring formation or chelation. From the observed frequency shifts the energy of these hydrogen bonds is estimated to be about 7 kcal. per mole. No evidence for unchelated molecules was found even in very dilute solutions of peracetic acid in nonpolar solvent nor in the vapour at low pressure and moderate temperature. Tentative assignments of the other frequencies in the spectra of the peracids are made by comparison with those of formic and acetic acids.The danger involved in handling these peracids in concentrated form is emphasized.

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