Double bonds infrared frequencies

Tertiary pyrrolines (49, = 1) and piperideines (49, = 2) (if R = H and the enamine can exist in the monomeric form or if R = aryl) evidently possess an endocyclic -double bond (79,155,156). The stretching frequency of the double bond can be lowered to 1620-1635 cm by conjugation with an aromatic substituent. The double bond of an analogous compound with aliphatic substituents in position 2 may occupy either the endo or the exo position. Lukes and co-workers (157) have shown that the majority of the five-membered-ring compounds, traditionally formulated with the double bond in a position, possess the structure of 2-alkylidene derivatives (50) with an exocyclic double bond, infrared absorption at 1627 cm . Only the 1,2-dimethyl derivative (51) is actually a J -pyrroline, absorbing at 1632 cm . For comparison, l,3,3-trimethyl-2-methylene pyrrolidine (52) with an unambiguous exocyclic double bond has been prepared (54). 

Complex formation results in a downfield change in the chemical shift of the methyl protons and a decrease in the double-bond infrared stretching frequency from 1680 to 1532 cm h In the presence of a small excess of PdCl2, the complex is rapidly converted to hexamethylbenzene and palladium chloride. 

Reaction of liquid 1,3-butadiene with solid CuCl (285) produces the complex (C4He)(CuCl)2. The infrared spectrum of this complex has bands at 1570 and 1507 cm which are considered to represent the C=C stretching frequencies of free and coordinated double bonds, respectively. Addition of 1,5-hexadiene to a solution of CuCl in concentrated HCl yields a white, rather unstable complex (C6Hio)(CuCl)2 (283). Complex formation results in a shift in the double-bond stretching frequency from 1640 to 1545 cm and the overall simplicity of the infrared spectrum suggests a trans configuration for the diene. 

In Table VII are recorded mean values for in a number of ethylene-metal carbonyl complexes and parent metal carbonyls as well as values for the double-bond infrared stretching frequency rc c the magnetic shielding parameter t for ethylene in those transition metal complexes for which data are available. Although with the metal carbonyl complexes, differences of geometry, oxidation state, etc., do not permit a correlation to be drawn between the absolute values of rco and for the various complexes, it is quite apparent from the tabulated data for the Mo, Mn, and Fe complexes that for a given metal. 

Infrared IR spectroscopy is quite useful in identifying carboxylic acid derivatives The, carbonyl stretching vibration is very strong and its position is sensitive to the nature of IKT the carbonyl group In general electron donation from the substituent decreases the double bond character of the bond between carbon and oxygen and decreases the stretch mg frequency Two distinct absorptions are observed for the symmetric and antisym metric stretching vibrations of the anhydride function... 

Table 7.24 Absorption Frequencies of Other Double Bonds Table 7.25 Absorption Frequencies of Aromatic Bands Table 7.26 Absorption Frequencies of Miscellaneous Bands Table 7.27 Absorption Frequencies in the Near Infrared Table 7.28 Infrared Transmitting Materials...

The structure of the protonated enamines has been investigated by infrared spectroscopy. On protonation there is a characteristic shift of the band in the double-bond stretching region to higher frequencies by 20 to 50 cm with an increased intensity of absorption (6,13,14a). Protonated enamines also show absorption in the ultraviolet at 220-225 m/x due to the iminium structure (14b). This confirms structure 5 for these protonated enamines, because a compound having structure 4 would be expected to have only end absorption as the electrons on nitrogen would not be available for interaction with the n electrons of the double bond. 

The infrared (IR) spectra of these compounds were mostly studied in the solid state which showed all the basic peaks characteristic of various functionalities attached to such bicyclic heterocycles with bridgehead nitrogen atoms. The difference in the frequency of carbonyl and carbon nitrogen double bond in tautomers of compound 18 (R = H) has been discussed previously in CHEC-II(1996) <1996CHEC-II(8)713>. 

The infrared spectra of several of these complexes confirm that the olefin exists, with its double bond, in the complex (35, 177, 178), but that the double bond is weakened by complex formation, as shown by the decrease of some 140 cm-1 in the C C stretching frequency (35). The total platinum-olefin bond order is approximately 4/3 (35), and the C C bond order approximately 5/3 (126). 

The tertiary enamines, in contrast to the secondary derivatives, cannot exhibit enamine-imine tautomerism. As the free bases, they exist only in the vinylamino form. Their physico-chemical properties are in agreement with this structure, especially the spectral properties. The bands due to the stretching frequency of the carbon-carbon double bond in their infrared spectra1-25-27 (situated at 1630-1660 cm-1 according to the nature of the substituents) occur at somewhat lower frequencies, but their intensities are greatly increased in comparison to those of simple olefins because of conjugation with the free electron pair on the nitrogen atom. Indications of cis-trans isomerism... 

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