Stretching bands

To date, the IR-CRLAS studies have concentrated on water clusters (both FI2O and D2O), and methanol clusters. Most importantly, these studies have shown that it is in fact possible to carry out CRLAS in the IR. In one study, water cluster concentrations in the molecular beam source under a variety of expansion conditions were characterized [34]- hr a second study OD stretching bands in (020) clusters were measured [35]. These bands occur between 2300... 

Figure Bl.22.1. Reflection-absorption IR spectra (RAIRS) from palladium flat surfaces in the presence of a 1 X 10 Torr 1 1 NO CO mixture at 200 K. Data are shown here for tluee different surfaces, namely, for Pd (100) (bottom) and Pd(l 11) (middle) single crystals and for palladium particles (about 500 A m diameter) deposited on a 100 A diick Si02 film grown on top of a Mo(l 10) single crystal. These experiments illustrate how RAIRS titration experiments can be used for the identification of specific surface sites in supported catalysts. On Pd(lOO) CO and NO each adsorbs on twofold sites, as indicated by their stretching bands at about 1970 and 1670 cm, respectively. On Pd(l 11), on the other hand, the main IR peaks are seen around 1745 for NO (on-top adsorption) and about 1915 for CO (tlueefold coordination). Using those two spectra as references, the data from the supported Pd system can be analysed to obtain estimates of the relative fractions of (100) and (111) planes exposed in the metal particles [26].

Aryl and vinyl esters C=C—0—CO—alkyl 1800-1750 The C=C stretching band also shifts to... 

Table 21 Monosubstituted Heterocycles Ring Stretching Bands in the 1600-1300 cm Region...

Fig. 4.59. Raman spectrum of methyl mercaptan (a) and SERS spectrum of methyl mercaptide (b) formed by adsorption ofthe mercaptan on a silver surface. The surface reaction is proven by the disappearance ofthe S-H stretching and bending bands at 2575 cm" and 806 cm", respectively. The Raman shift ofthe C-S stretching band at approximately 700 cm" is reduced during adsorption by withdrawal of electron density from the C-S, because of bonding to the silver. The symmetric methyl stretching appears above 2900cm" [4.303].

Compound A undergoes hydrolysis of its acetal function in dilute sulfuric acid to yield 1,2-ethanediol and compound B (CgHg02), mp 54°C. Compound B exhibits a carbonyl stretching band in the infrared at 1690 cm and has two singlets in its H NMR spectrum, at 8 2.9 and 6.7, in the ratio 2 1. On standing in water or ethanol, compound B is converted cleanly to an isomeric substance, compound C, mp 172—173°C. Compound C has no peaks attributable to carbonyl groups in its infrared spectrum. Identify compounds B and C. 

The infrared spectra of alcohols change markedly with increasing concentration. For example, at very low concentration, the infrared spectrum of te/t-butyl alcohol in carbon tetrachloride contains a single sharp band at approximately 3600 cm corresponding to the OH stretching motion. As the alcohol s concentration increases (by adding more alcohol to the sample), a second broad OH stretch band grows in at approximately 3400 cm and eventually replaces the other band. 

Trimethyl-2-pteridinone (22) has acidic properties pKa 10.26) and hence must be hydrated in the anion. The neutral species exhibits a NH-stretching band at 3414 cm in chloroform solution and hence must be at least partly hydrated. The suggestion that the hydroxyl group is attached to C-7 needs to be confirmed. Fidler and Wood prepared several analogues of 22 and noted their affinity for water, which they considered not to be covalently bound in the neutral... 

Both the infrared and ultraviolet spectra of pyrrolidine-2,3,5-triones (75) have been interpreted to support their existence as hydroxy-maleimides (76), and the occurrence of a strong OH stretching band in the infrared spectrum of 4-phenylpyrrolidine-2,3,5-trione has been taken as evidence that it too exists in a hydroxy form, probably 76 (R CeHg). However, the trioxo formulation is suggested by t/j the infrared spectra of jV-substituted pyrrolidine-2,3,5-triones, although an equilibrium apparently occurs depending upon the substituents and conditions. The zwitterion formulation 77 has been advanced for 4-aminopyrrolidine-2,3,5-trione. For chemical evidence... 

The substituted 3-aminofurans (91, R = H, Me) resinify in air, can be diazotized (structure 91), and are easily hydrolyzed (structure 92 ). ° The infrared spectra of both 2- and 3-acctamidofuran show a strong NH stretching band indicating that these compounds do, indeed, exist in the acetamido form. ... 

IR analysis can also be used quantitatively to determine the EO-PO ratio [12]. Using mixtures of polyethylene glycol and polypropyene glycol as calibration standards, the ratio of two absorbances, one due to the methyl group of the PO unit (e.g., the C-H stretch band at 2975 cm ) and one due to the methylene group (e.g., the C-H stretch band at 2870 cm ), are plotted against percent of PO content. The ratio of the same two absorbances taken from the IR spectrum of a poloxamer may then be used to determine its percent of PO content by interpolation. 

Distinguishing between the fac- and mer-isomers is theoretically possible with far-IR spectra, as the mer-isomer (C2v symmetry in the coordination sphere) should give rise to three u(Os—X) stretching bands, while the C3v... 

The correlation analysis of infrared data has been much examined by Katritzky, Topsom and colleagues69,70. Thus, the intensities of the v16 ring-stretching bands of mono- and di-substituted benzenes may be correlated with the oR° values of the substituents and these correlations may be used to find new oR° values. 

Metal-ligand vibrations have been identified using metal isotopes, e.g. the Ni—P stretching band which appears at 273.4 cm for NiCl2(PEt3)2 is shifted to 267.5 cm" for the Ni complex. 

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