A Low Temperature Infrared Study on the Association of Thiols with Pyridine and Triethylamine

The infrared spectra of solutions containing propane-1-thiol or benzenethiol as proton donors, and pyridine or triethylamine as proton acceptors were measured down to about −100 °C. The dependence of hydrogen bond formation on concentration and temperature was studied at the fundamental and overtone region of the S—H stretching vibration. The predominant species is found to be a 1:1 [Formula: see text] type complex. In addition, evidence was found for the existence of more highly associated species at low temperatures. Thiol–thiol [Formula: see text] type hydrogen bonds are also present in the case of benzenethiol–pyridine mixtures.

Download Full-text

A Low Temperature Infrared Study of Self-association in Thiols

Canadian Journal of Chemistry ◽

10.1139/v72-574 ◽

1972 ◽

Vol 50 (22) ◽

pp. 3594-3600 ◽

Cited By ~ 15

Author(s):

R. Bicca de Alencastro ◽

C. Sandorfy

Keyword(s):

Hydrogen Bonding ◽

Low Temperature ◽

Infrared Spectra ◽

Low Temperatures ◽

Infrared Study ◽

Text Type ◽

Stretching Vibration ◽

Aliphatic Thiols ◽

Self Association ◽

Associated Species

The infrared spectra of several aliphatic thiols and of benzenethiol were measured between 2400 and 2700 cm−1, and 4800 and 5300 cm−1 in a 1:1 mixture of CCl3F and C2F4Br2, at temperatures ranging from 20 to −190 °C. Dimerization takes place at low temperatures and more highly associated species also appear. Free S—H groups are present in the solutions as well as in the pure liquids, even at the lowest temperatures. The association is of the [Formula: see text] type in aliphatic thiols; both [Formula: see text] and [Formula: see text] bonds are found in the case of benzenethiol and α-toluenethiol. Hydrogen bonding has little effect on the anharmonicity of the S—H stretching vibration.

Download Full-text

A Low-temperature Infrared Study of Self-association in Thiolic Acids

Canadian Journal of Chemistry ◽

10.1139/v73-218 ◽

1973 ◽

Vol 51 (9) ◽

pp. 1443-1447 ◽

Cited By ~ 8

Author(s):

R. Bicca de Alencastro ◽

C. Sandorfy

Keyword(s):

Low Temperature ◽

Low Temperatures ◽

Carbonyl Groups ◽

Infrared Study ◽

Text Type ◽

Stretching Vibration ◽

Self Association ◽

High Concentrations ◽

Associated Species ◽

Anharmonicity Constants

The i.r. spectra of thioloacetic and thiolobenzoic acids were measured in both the fundamental and first overtone regions of the S—H stretching vibration, in a mixture of CCl3F and C2F4Br2, at temperatures ranging from 20 to −190 °C. [Formula: see text] type bonds are formed at low temperatures or at high concentrations of solute. Two different species can be detected. The first is probably an open dimer and the second a cyclic dimer. The S—H anharmonicity constants are of the order of 50–60 cm−1, for both free and associated species, and have about the same value as in aliphatic or aromatic mercaptans. Carbonyl groups have lower anharmonicities. Their value is about 10 cm−1, for both free and associated species.

Download Full-text

A Low Temperature Infrared Study of Hydrogen Bonding in N-Alkylacetamides

Canadian Journal of Chemistry ◽

10.1139/v73-541 ◽

1973 ◽

Vol 51 (21) ◽

pp. 3640-3646 ◽

Cited By ~ 35

Author(s):

Marie-Claude Bernard-Houplain ◽

C. Sandorfy

Keyword(s):

Hydrogen Bond ◽

Hydrogen Bonding ◽

Low Temperature ◽

Infrared Spectra ◽

Bond Formation ◽

Coupling Constant ◽

Infrared Study ◽

Hydrogen Bond Formation ◽

Stretching Vibration ◽

Secondary Amides

The infrared spectra of N-methylacetamide and two other secondary amides were measured in solution at temperatures ranging from 22 to −190 °C in both the fundamental and the overtone regions. At least two hydrogen bonded species are found as association increases with decreasing temperature. The effect of hydrogen bond formation on the anharmonicity of the NH stretching vibration and on the NH stretching – NH bending coupling constant is examined.

Download Full-text

An infrared study of the interaction between ethyl N-(diphenylmethylene)glycinate with proton donors: comparison with N-benzylidenemethylamine

Canadian Journal of Chemistry ◽

10.1139/v86-378 ◽

1986 ◽

Vol 64 (12) ◽

pp. 2305-2309 ◽

Cited By ~ 6

Author(s):

Marleen Ruysen ◽

Thérèse Zeegers-Huyskens

Keyword(s):

Hydrogen Bond ◽

Ir Spectra ◽

Equilibrium Constants ◽

Lone Pair ◽

Imino Group ◽

Infrared Study ◽

Hydrogen Bond Formation ◽

Hydroxy Proton ◽

Proton Donors ◽

Intramolecular Hydrogen

The interaction between ethyl N-(diphenylmethylene)glycinate (DPG) and hydroxy proton donors or pyrrole has been investigated by ir spectrometry. The equilibrium constants, enthalpies, and entropies of complex formation have been determined in carbon tetrachloride solution and compared with the data obtained for the complexes involving N-benzylidene-methylamine and the same proton donors. The ir spectra studied mainly in the νOH, νC=N, νC=O, and νC—O regions suggest that hydrogen bond formation occurs at the N atom of the imino group and at the O atom of the carbonyl group. The results are discussed in terms of the basicity at the two acceptor sites and of the accessibility of the lone pair of electrons. The ir spectra of the solid adduct of DPG with HCl show that protonation takes place on the N atom. The protonated structure is possibly stabilized by an intramolecular hydrogen bond.

Download Full-text

Anharmonicity, solvent effects, and hydrogen bonding: NH stretching vibrations

Canadian Journal of Chemistry ◽

10.1139/v70-367 ◽

1970 ◽

Vol 48 (14) ◽

pp. 2197-2203 ◽

Cited By ~ 8

Author(s):

A. Foldes ◽

C. Sandorfy

Keyword(s):

Hydrogen Bond ◽

Hydrogen Bonding ◽

Solvent Effects ◽

Bond Formation ◽

Hydrogen Bond Formation ◽

Stretching Vibration ◽

Solvent Shifts ◽

Stretching Vibrations ◽

Secondary Amides ◽

Influence Of Solvent

The influence of solvent effects and hydrogen bond formation on the anharmonicity of the NH stretching vibration of simple secondary amides, lactams, anilides, indole, pyrrole, and imidazole have been studied; and the frequencies of the first and second overtones, their half widths and solvent shifts measured. The validity of Buckingham's theory is established in the case of inert solvents; whereas the second order perturbation treatments are shown to be inapplicable to the case of hydrogen bonding solvents. All NH stretching modes seem to exhibit the same anharmonic behavior which is very different from that of OH vibrations.

Download Full-text

Low Temperature Infrared Study of Hydrogen Bonding in Dissolved Pyrrole and Indole

Canadian Journal of Chemistry ◽

10.1139/v73-159 ◽

1973 ◽

Vol 51 (7) ◽

pp. 1075-1082 ◽

Cited By ~ 48

Author(s):

Marie-Claude Bernard-Houplain ◽

C. Sandorfy

Keyword(s):

Hydrogen Bonding ◽

Low Temperature ◽

Spectroscopic Methods ◽

Infrared Study ◽

Stretching Vibration ◽

Self Association ◽

Associated Species

Self-association by hydrogen bonding in the case ot pyrrole was studied by i.r. spectroscopic methods. The fundamental first and second overtones of the NH stretching vibration were measured at different concentrations and at temperatures ranging from 22 to −190 °C. The existence of at least two associated species in solution has been ascertained. 2,5-Dimethylpyrrole and indole were also studied and gave similar results.

Download Full-text

Fourier Transform Raman and DFT Study of Blue Shift C–H Stretching Vibration of Diazines on Hydrogen Bond Formation

Zeitschrift für Physikalische Chemie ◽

10.1524/zpch.2011.0081 ◽

2011 ◽

Vol 225 (6-7) ◽

pp. 785-798 ◽

Cited By ~ 3

Author(s):

Deepa Singh ◽

Jürgen Popp ◽

Ranjan K. Singh

Keyword(s):

Hydrogen Bond ◽

Fourier Transform ◽

Bond Formation ◽

Blue Shift ◽

Dft Study ◽

Hydrogen Bond Formation ◽

Stretching Vibration ◽

Fourier Transform Raman

Download Full-text

The Solubility of Acetylene in Various Organic Solvents under High Pressures and at Low Temperatures. VII. Hydrogen Bond Formation between Acetylene and Donor Solvents

Nippon kagaku zassi ◽

10.1246/nikkashi1948.82.5_520 ◽

1961 ◽

Vol 82 (5) ◽

pp. 520-523 ◽

Cited By ~ 1

Author(s):

Bunkichi RYUTANI

Keyword(s):

Hydrogen Bond ◽

Organic Solvents ◽

Low Temperatures ◽

High Pressures ◽

Bond Formation ◽

Hydrogen Bond Formation

Download Full-text

Vapochromism induced by intermolecular electron transfer coupled with hydrogen-bond formation in zinc dithiolene complex

Journal of Materials Chemistry C ◽

10.1039/d0tc04280c ◽

2020 ◽

Vol 8 (42) ◽

pp. 14939-14947

Author(s):

So Yokomori ◽

Shun Dekura ◽

Tomoko Fujino ◽

Mitsuaki Kawamura ◽

Taisuke Ozaki ◽

...

Keyword(s):

Hydrogen Bond ◽

Electron Transfer ◽

Bond Formation ◽

Intermolecular Electron Transfer ◽

Hydrogen Bond Formation ◽

Complex Crystal

A novel vapochromic mechanism by intermolecular electron transfer coupled with hydrogen-bond formation was realized in a zinc dithiolene complex crystal.

Download Full-text