Hydrogen frequency shifts

Obviously, this shift implies the self-association of DMSO. Further frequency shifts to even lower wave numbers (1050-1000 cm " ) are observed in both aprotic polar and protic solvents. In aprotic solvents such as acetonitrile and nitromethane, the association probably takes place between the S—O bond of DMSO and the —C=N or the —NOz group in the molecules by dipole-dipole interaction as shown in Scheme 331,32. Moreover, the stretching frequency for the S—O bond shifts to 1051 cm 1 in CHC13 and to 1010-1000 cm -1 in the presence of phenol in benzene or in aqueous solution33. These large frequency shifts are explained by the formation of hydrogen bonds between the oxygen atom in the S—O bond and the proton in the solvents. Thus, it has been... 

A similar quantitative treatment of sulphoxides as hydrogen bonding acceptors has been obtained by comparing the IR frequency shift AvOH of the C—I bond in an acetylenic iodide such as IC=CI (Avc j) due to formation of a C—T complex with phenol in various bases. This investigation suggests that sulphoxides belong to the same family as carbonyls, phosphine oxides, arsine oxides and their derivatives90. 

Drago and coworkers have also calculated the enthalpy values for the formation of many complexes or hydrogen bonds by NMR and calorimetric techniques. For example, in a series of phenols or t-BuOH, they observed the IR frequency shifts (Avqh) of the hydroxyl compounds and found that a linear relationship exists between bases and individual acids. In Table 7 shows some AH values calculated by equation 2, and Avqh values of t-BuOH" " while in Table 8 frequency data Avq of various substituted phenols and the AH values are given. 

The evidence presented for the formation of hydrogen bonds with sulphoxides and sulphones was first reported by Barnard. Fabian and Koch, who measured the characteristic infra-red stretching frequency shifts of the S—O bond in the presence of MeOH in Simultaneously the OH stretching band of MeOH at... 

The frequencies of absorption bands present gives diagnostic information on the nature of functional groups in materials as well as information from any observed frequency shifts on aspects such as hydrogen bonding and crystallinity. In many cases, spectra can be recorded non-destructively using either reflection or transmission procedures. IR spectra of small samples can also be obtained through microscopes (IR microspectrometry). Chalmers and Dent [8] discuss the theory and practice of IR spectroscopy in their book on industrial analysis with vibrational spectroscopy. Standard spectra of additives for polymeric materials include the major collection by Hummel and Scholl [9]. 

Hagelin, J., T. Brinck, M. Berthelot, J. S. Murray, and P. Politzer. 1995. Family Dependent Relationships Between Computed Molecular Surface Quantities and Solute Hydrogen Bond Acidity/Basicity and Solute-Induced Methanol O-H Infrared Frequency Shifts. Can. J. Chem. 73, 483. 

There have been many studies on the formation of hydrogen bonds between alcohols and a wide range of bases. If the bases are of similar type (for example, all nitrogen donor atoms in amines), there is also frequently a rather good correlation between the shift of the O-H stretching band and other properties. For example, stretching frequency shifts of the OH bonds in alcohols have been correlated... 

Relationships between the stretching frequency shifts and hydrogen bond enthalpies have also been established. Such a correlation can be written in the form... 

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