Infrared Spectral Interpretation

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1 Infrared Spectral Interpretation i Wherever you see this symbol, it is important to access the on-line course as there is interactive material that cannot be fully shown in this reference manual.

2 1 Contents Page 1 Infrared Spectral Quality Orbital Hybridization sp, sp 2, and sp 3 Carbon sp 3 Hybridization sp 2 Hybridization sp Hybridization 6 3 General Infrared Interpretation Concepts IR Frequencies 9 5 Alkanes Alkenes Alkynes 14 8 Aromatic Compounds Alcohols The OH Group and Hydrogen Bonding Ethers Amines Carbonyl Frequencies Aldehydes Ketones Carboxylic Acids Esters Amides Anhydrides Acid Chlorides Fermi Resonance Stretching Frequencies Carbonyls Nitrogen Sulfur Phosphorus, Boron, and Halogen Inorganic 44 References 45

3 2 1. Infrared Spectral Quality Infrared interpretation must be performed on a high quality spectrum; otherwise, misleading results can be obtained. More often than not, bad sample preparation is the main cause of poor quality IR spectra. A high quality infrared spectrum must possess a flat (level) baseline (positioned near or around 100% transmittance and with a low level of noise). Shifting of the baseline position would indicate at least one of the following conditions: The background spectrum does not correspond to the sample spectrum (i.e. different solvent). The aperture size (where appropriate) for the background and sample spectra do not correspond. The sample strongly absorbs. The sample solvent absorbs strongly when obtaining spectra in the solution phase. The NaCl or KBr discs are cloudy. A sloping baseline usually indicates the electromagnetic radiation has been diffracted or scattered as it interacts with the sample. This may happen when the particles in the KBr pellet are not ground properly or if the sample surface of a thin film is not homogeneous (air bubbles etc.). Additional bands should be avoided, in particular, carbon dioxide and water which can absorb infrared radiation, therefore, their presence should be minimized (usually below 2% transmittance, Figure 1). This can be achieved by ensuring samples are made with dry solvents (solution IR), dry KBr (solid state IR), and by taking a background spectrum to account for atmospheric water and carbon dioxide within the instrument. Figure 1: IR background spectrum. Dispersive IR instruments are dual beam instruments with equivalent beams passing independently through both the sample and reference chambers. During analysis the sample and reference beams are alternately focused on the detector by an optical chopper, allowing for comparison and subtraction of the sample and reference spectra. Therefore, the reference chamber should be filled with the same matrix as the sample to account for any IR active components (solvent, water, CO 2 ). FTIR instruments are single beam instruments, therefore, before a sample spectrum is obtained a spectrum of the sample matrix is acquired which can be subtracted from the sample spectrum to

4 3 account for any IR active solvents or dissolved gases within the sample matrix which may obscure analytically relevant peaks in the sample spectrum. Remember: Water produces small, sharp absorption bands in the regions from and cm -1. Carbon dioxide produces a strong doublet near 2340 cm -1.

5 2. Orbital Hybridization sp, sp 2, and sp 3 Carbon 4 Hybridization is used to explain molecular structures and describes the various orbital types which are involved in the bonding between atoms. In infra-red analysis, the nature of the bonding can make a big difference to the region of the spectrum in which the signal appears, and as such, this brief refresher is intended to remind you of the concept of Orbital Hybridization which can be used to help interpret infrared spectra. Using carbon as an example it is known that for a tetrahedrally coordinated carbon (e.g. methane CH 4 ) the carbon atom will have four orbitals with the correct symmetry to bond to the four hydrogen atoms. With respect to IR spectroscopy, the energy of the infrared light absorbed by a C-H bond is dependent on the type of hybridization of the bonding orbitals. The C-H bond strengths are in the order sp 3 >sp 2 >sp, due to the increased s character of the hybrid orbital which results in better overlap with the hydrogen s-orbital. This results in the different IR stretching frequencies that are observed for sp 3, sp 2, and sp carbons. The orbitals that are used by carbon to form hybrid bonding orbitals are s- and p-orbitals (Figure 2). Figure 2: s- and p-orbitals sp 3 Hybridization The ground state configuration of carbon is 1s 2 2s 2 2px 1 2py 1. The p orbitals are equal in energy and said to be degenerate. The two singly occupied p orbitals can be utilized for bonding to give methylene CH 2, an unstable free radical (Figure 3). Excitation of an electron from the doubly occupied 2s orbital to the empty 2p orbital results in four singly occupied orbitals. Excitation of an electron from the 2s to the 2p orbital requires an input of energy; this is offset by the release of energy that is obtained by the formation of the two additional bonds, making this an energetically favored process. Quantum mechanics states that the lowest energy will be obtained if the four bonds are equivalent which requires that they are formed from equivalent orbitals on the carbon. Therefore, a set of four equivalent orbitals can be obtained via hybridization of the valence-shell (core orbitals that are not involved in bonding) s- and p-orbitals to form four sp 3 orbitals, each consisting of 25% s character and 75% p character (Figure 3). The hybrid orbitals are orientated at a bond angle of from each other, giving tetrahedral geometry as seen in methane (Figure 4). In methane the four sp 3 hybrid orbitals will overlap with the hydrogen 1s orbital resulting in four covalent bonds (σ bonds) which will be of equal length and have equal bond strengths.

6 5 Figure 3: Formation of sp 3 hybrid orbitals. Figure 4: Molecular geometry arising from sp 3 hybridization, for example in methane sp 2 Hybridization sp 2 hybridization results in the formation of molecules with trigonal planar structures (e.g. aluminium trihydride). The three sp 2 hybridized orbitals are formed as follows (Figure 5): Figure 5: Formation of sp 2 hybrid orbitals. Each of the three sp 2 orbitals has 33% s character and 67% p character. The orbitals are orientated to minimize electron repulsion giving bond angles of 120. The p-orbital that is not used to form the hybrid orbitals remains unchanged and sits perpendicular to the plane of the three sp 2 orbitals (Figure 6). In compounds such as alkenes there is a double bond between the carbon atoms, i.e. ethene C 2 H 2. In the case of ethene, two of the sp 2 hybridized orbitals (on each of the individual carbon atoms) are used to form σ bonds with the 1s orbitals on hydrogen. The remaining sp 2 orbitals on each of the carbon atoms overlap to form a C-C σ-bond. The remaining two p-orbitals contain a single electron; overlap of these orbitals forms a π-bond, creating a double bond between the two carbon atoms. The double bond results in ethene having linear geometry with the carbon atoms being trigonal planar (Figure 6).

7 sp Hybridization Figure 6: Geometry and bonding resulting from sp 2 hybridization. The linear geometry of molecules such as alkynes can be explained by sp hybridization. The 2s orbital and one 2p orbital hybridize to form two sp hybrid orbitals, which will each have 50% s and 50% p character (Figure 7). These orbitals are aligned to minimize electron repulsion and give a bond angle of 180, as seen in linear molecules (Figure 8). There are two remaining p-orbitals that contain a single electron that can be utilized by the molecule. As in sp 2 hybridization these p-orbitals are orientated perpendicular to the two sp orbitals. Figure 7: Formation of sp hybrid orbitals. The singly occupied p-orbitals can be used in molecules such as ethyne to form two additional π- bonds resulting in a triple bond. This can only occur when two atoms, such as carbon, both have two p-orbitals that each contains a single electron (Figure 8). Figure 8: Geometry and bonding resulting from sp hybridization.

8 7 3. General Infrared Interpretation Concepts In order to infer any useful information from an infrared spectrum, it is necessary, not only to identify the region in which signals appear, but also their shape and intensity. In general terms: Band frequency: indicates the presence of functional groups. Band shape: provides information on functional groups as well as purity. Single absorptions are symmetric, so deviations in symmetry (such as shoulders or tailing) would indicate overlapping. Band intensity: indicates the type and amount of functional groups within the molecule. The following rules will help you to interpret any mid-infrared spectrum: Band frequency assignment is usually straightforward in the region ( cm -1 ) and more difficult in the fingerprint region ( cm -1 ) (Figure 9). Figure 9: IR spectrum with analytically relevant regions indicated. For each band, make a list of possible functional groups. Since most organic compounds have C-H bonds, a useful rule is that absorption between 2850 and 3000 cm -1 is due to sp 3 C-H stretching; whereas, absorption above 3000 cm -1 is from sp 2 C- H stretching or sp C-H stretching if it is near 3300 cm -1.

9 8 Figure 10: Position of unsaturated and aliphatic C-H stretching frequencies. Cross-checking whenever possible. For example, an organic alcohol should exhibit O-H and C-O stretching bands. Do not expect to be able to assign every single band in the spectrum. For a given functional group, band intensities may vary considerably. Infrared spectroscopists have classified the intensity of signals in four groups (Figure 11): Strong signals (s): when signal intensity is approximately 5% T. Medium signals (m): when signal intensity is between 30 and 60% T. Weak signals (w): when signal intensity does not exceed 70% T. Variable signals (v): signal strength may vary depending on the particular molecular structure, presence of hydrogen bonding, state of the sample (solid, liquid etc.). Figure 11: Classification of IR signals (oversimplified). The following pages will detail the major IR spectroscopic features that can be used in structural elucidation.

10 9 4. IR Frequencies The interpretation of infrared spectra can be aided by an overview of the major signals of interest as is presented below (Figure 12). Whilst the diagram is by no means comprehensive, it is intended to be a guide for beginners to recognize the major features of common infrared spectra. The topics which follow will highlight more specific spectral features generated by some common functional groups. Figure 12: Infrared frequencies of selected functional groups. 1-2

11 10 5. Alkanes The spectra of alkanes are usually simple (few peaks, Figure 13). The sp 3 C-H stretch occurs at frequencies not exceeding 3000 cm (s) (w) Two or three bands C-H stretching (m) C-H deformations (m) CH 3 symmetrical deformation ~720(w) -CH 2 rocking Table 1: Important frequencies in alkanes. REMEMBER: (s) strong signal (~5% T), (m) medium signal (~ 40% T), (w) weak signal (~70% T), (v) variable. i Figure 13: The infrared spectrum of octane.

12 11 Wavenumber (cm -1 ) Explanation 2850 CH 3 symmetric and asymmetric stretch 1450 Aliphatic CH 2 bending (scissoring) 1380 Aliphatic CH 3 bending (symmetrical) 720 Aliphatic CH 2 rocking Table 2: Octane IR frequencies.

13 12 6. Alkenes The spectra of alkenes are usually more complex (more peaks) than the spectra of alkanes (Figure 14). The sp 2 C-H stretch occurs at frequencies above 3000 cm -1. Symmetrically substituted double bonds do not absorb in the infrared region (m) (m) C-H stretching (sp 2 absorption). Often obscured by the stronger bands of saturated C-H groups (s) C-H out of plane deformation 1416 C-H in plane bending Non-conjugated C=C stretching (v) May be very weak if symmetrically substituted Table 3: Important frequencies in alkenes. i Figure 14: The infrared spectrum of cis-2-pentene. Wavenumber (cm -1 ) Explanation 2950 C-H stretching (sp 2 absorption) 2850 CH 3 symmetric and asymmetric stretch 1600 C=C stretch 700 =C-H out of plane bending Table 4: Cis-2-pentene IR frequencies.

14 (s) (s) (s) (s) (m) (m) Table 5: Alkene C-H out of plane deformations. C=C (v) Non-conjugated C=C stretching May be very weak if symmetrically substituted Conjugated with aromatic ring 1625(m) Dienes, trienes etc. 1650(s) and 1600(s) Overlap of bands is common with the low frequency band being more intense α,β-unsaturated carbonyl (s) Weaker than C=O Enol esters, enol ethers, and enamines (s) Table 6: Alkene C=C vibrations. Figure 14b: Alkene containing compounds.

15 14 7. Alkynes Terminal alkynes exhibit strong C-H and C C signals near 3300 and 2150 cm -1 respectively (non-terminal alkynes tend to lack such signals). The alkyl chain will exhibit similar IR frequencies to alkanes. Symmetrically substituted triple bonds do not absorb in the infrared region. In the case of octyne (Figure 16) the alkyne bond is asymmetrically substituted, therefore, it will be IR active. 3300(m) C-H stretching (sp absorption) C-H out of plane bending (w) C C stretch (v) C C stretch (s) Isonitriles Nitrile oxides ~2260 Diazonium salts Thiocyanates Aryl substitutes at the upper end of the range (s) and alkyl at the lower end Table 7: Important frequencies in alkynes. i Figure 16: The infrared spectrum of 1-octyne. Wavenumber (cm -1 ) Explanation 3300 C-H stretching (sp absorption) 2850 CH 3 symmetric and asymmetric stretch 2150 Asymmetric C=C stretch 600 =C-H out of plane bending Table 8: 1-Octyne IR frequencies.

16 15 8. Aromatic Compounds The aromatic sp 2 =C-H stretch occurs at frequencies beyond 3000 cm -1 (Figure 18). The out of plane =C-H stretch is usually intense and occurs at cm -1. Overtone/combination bands at cm (m) C-H stretching (sp 2 absorption) C-H in-plane bending (s) ~1600(m) ~1580(m) ~1500(m) C-H out of plane bending Aromatic C=C Stretch Table 9: Important frequencies in aromatic compounds. The IR stretching frequencies found in the region cm -1, produced by the C-H out-of-plane bending modes, are highly characteristic of the aromatic substitution pattern (Figure 17). Figure 17: Aromatic substitution (oversimplified).

17 16 i Figure 18: The infrared spectrum of toluene. Note that the aromatic C-H stretches are to the left of 3000 cm -1 and the alkyl C-H stretches are to the right. Wavenumber (cm -1 ) Explanation 3010 Aromatic C-H stretching (sp 2 absorption) 2850 CH 3 symmetric and asymmetric stretch Aromatic overtone/combination bands Aromatic C=C stretch =C-H out of plane bending Mono substitution pattern Table 10: Toluene IR frequencies. Aromatic rings ~1600(m) ~1580(m) Stronger when the ring is further conjugated ~1500(m) Usually the strongest of the 2 or 3 bands Table 11: Aromatic compounds.

18 17 R-C 6 H (s) and (s) Monosubstituted Disubstituted R 2 -C 6 H (s) Ortho (s), (m) Meta (s) Para R 3 -C 6 H 3 R 4 -C 6 H (s), (m) (m), (s) (s), (m) (s) (s) (s) Trisubstituted 1,2,3-1,2,4-1,3,5- Tetrasubstituted 1,2,3,4-1,2,3,5-1,2,4,5- R 5 -C 6 H (m-s) Pentasubstituted R 6 -C (m-s) Hexasubstituted Table 12: Benzene ring substitution patterns. Figure 19: Benzene substitution patterns.

19 18 9. Alcohols The free OH band appears as a sharp signal of medium to low intensity near 3620 cm -1. This band usually appears when the alcohol is dissolved in a solvent (Figure 20). The hydrogen bonded OH band appears as a broad peak between 3400 and 3300 cm -1. This band usually appears when the alcohol is not dissolved in a solvent. The hydrogen bonded and the free OH bands are present together with the relatively weak free OH signal appearing to the left or completely overlapped by the hydrogen bonded signal (v) Free OH stretch (sharp peak) (s) H-bonded OH (solid, liquid, and dilute solution, broad band) (v) Intramolecular H-bonded OH in chelate form (broad) (w) Water of crystallization (solid state spectra) (s) OH bending C-O stretching Table 13: Important frequencies in aromatic compounds. i Figure 20: The infrared spectrum of 1-hexanol.

20 19 Wavenumber (cm -1 ) Explanation 3650 Free OH stretch Hydrogen bonded OH stretch 2850 CH 3 symmetric and asymmetric stretch 1465 Aliphatic CH 2 bending (scissoring) 1365 Aliphatic CH 3 bending (symmetrical) 1100 C-O stretching 720 Aliphatic CH 2 rocking Table 14: 1-Hexanol IR frequencies.

21 The OH Group and Hydrogen Bonding The stretching frequency of OH groups can be used to measure the strength of hydrogen bonds. The stronger the hydrogen bond the longer the OH bond will be, resulting in a lower vibrational frequency, and a broader and more intense absorption band. Sharp free monomeric OH bands ( (v) cm -1 ) will often be seen when there is little possibility for hydrogen bonding i.e. in the vapor phase, dilute solutions, and when steric hindrance precludes H bonding. Pure liquids, solids, and solutions will often only exhibit a broad polymeric H bonded band for the OH group ( (s) cm -1 ). However, liquids will sometimes show both monomeric and polymeric bands. A good diagnostic test of whether an inter- or intramolecular H bond is present is to dilute the solution; intramolecular H bonds will be unaffected, and therefore, the absorption band will remain unchanged, whereas, intermolecular bonds will be broken resulting in a decrease in the H-bonded OH absorption and an increase in, or appearance of, a free OH band. Figure 21: The O-H stretch region. (a) Hydrogen-bonded O-H only (neat liquid). (b) Free and hydrogen-bonded O-H (dilute solution). (c) Free and hydrogen-bonded O-H (very dilute solution).

22 Ethers The spectra of ethers are usually simple. The main difference between the IR spectra of ethers and alcohols is that ethers lack O-H signals. The C-O stretching allows for the differentiation of ethers from alkanes (Figure 22) (s) C-O stretching (s) (s) (m) (s) C-O stretching alkyl aryl ether C-H stretching aryl ethers at high end of the range (s) (m-s) (m) Monosubstituted (v) Trans form (m) Cis form (s) Trisubstituted Table 15: Important frequencies in ethers. i Figure 22: The infrared spectrum of dibutyl ether.

23 22 Wavenumber (cm -1 ) Explanation 2850 CH 3 symmetric and asymmetric stretch 1480 Aliphatic CH 2 bending (scissoring) 1320 Aliphatic CH 3 bending (symmetrical) 1100 C-O stretching 720 Aliphatic CH 2 rocking Table 16: Dibutyl ether IR frequencies.

24 Amines Primary amines have two N-H bands in the range cm -1 corresponding to symmetrical and unsymmetrical stretching (Figure 23-24). Figure 23: N-H stretching frequencies in primary (left) and secondary (right) amines. Secondary amines absorb weakly and have one N-H band in the range cm -1. Tertiary amines lack N-H signals (m) Amine and imine N-H stretching (m) N-H bend in primary amines result in a broad band (w) N-H bend in secondary amines 1600(s) 1500(s) Secondary amine salts exhibit a 1600 cm -1 band ~800 N-H out of plane bending C-N stretch Table 17: Important frequencies in amines.

25 24 i Figure 24: The infrared spectrum of n-hexylamine. Wavenumber (cm -1 ) Explanation 3500 NH 2 symmetric and asymmetric stretch 2850 CH 3 symmetric and asymmetric stretch 1600 N-H bending 1480 Aliphatic CH 2 bending (scissoring) 1320 Aliphatic CH 3 bending (symmetrical) 1100 C-N stretching 800 N-H out of plane bending 720 Aliphatic CH 2 rocking Table 18: N-hexylamine IR frequencies. N-H bands can often be confused with OH bands, however, due to their lower propensity for forming hydrogen bonds the bands will be sharper which can aid in identification. N-H absorption is of weaker intensity (m) Aliphatic (w-m) α-carbon branching at 795 cm (w-m) Strong (m-s) Broad Aromatic (s) Also for secondary aryl amines (m) Solid state Amino acids (m) (m) Sharp bands; dilute solution 1550(m) Table 19: Primary, secondary, and tertiary amines.

26 Carbonyl Frequencies Composed of a carbon atom double bonded to an oxygen atom, carbonyl groups absorb energy in the infrared region between approximately 1600 to 1900 cm -1 (Figure 25). Weak bands, overtones of the strong C=O absorption ( cm -1 ) appear in the cm -1 region. Figure 25: IR frequency values for selected carbonyl compounds. Electron-Withdrawing Effect: electron withdrawing centers next to the carbonyl group will shift its frequency to higher values. Figure 26: The electron withdrawing effect will shift the carbonyl band to higher frequencies. Further conjugation has relatively little effect. When one or more of the structural influences is affecting a carbonyl group the effect is close to additive. Carbonyl intensities: Acids absorb more strongly than esters. Esters absorb more strongly than ketones or aldehydes. Hydrogen Bonding Effect: Intramolecular hydrogen bonding will shift the carbonyl signal to lower frequencies. In the diagram below, the molecule methyl salicylate (an ester) exhibits an unusually low carbonyl frequency of 1680 cm -1 instead of being between 1735 and 1750 cm -1. This phenomenon is due to the formation of an intra-molecular hydrogen bond. Figure 27: The hydrogen bonding effect will shift the carbonyl band to lower frequencies.

27 26 Resonance Effect: when the unpaired electrons on a nitrogen atom conjugate with the carbonyl group, then the carbonyl band is shifted to a lower frequency. Figure 28: The resonance effect will shift the carbonyl band to lower frequencies. Ring Size: six-membered rings with carbonyl groups will exhibit similar frequencies to their noncyclic counterparts; however, decreasing the ring size (rings with less than six members) will increase the frequency of the carbonyl absorption.

28 Aldehydes The spectra of aldehydes usually contain strong C-O stretching bands between 1740 and 1680 cm -1 (Figure 29). Aldehydes exhibit a pair of C-H stretching bands; however, while the lower frequency ( cm -1 ) signal is usually found in most spectra, the one at high frequency values ( cm -1 ) is usually obscured by alkyl C-H signals (s) Aliphatic C=O stretching (s) Aromatic C=O stretching (w) C-H aldehyde stretch consists of a pair of weak signals (one of them is usually obscured by alkyl signals) Table 20: Important frequencies in aldehydes. i Figure 29: The infrared spectrum of nonanal. Wavenumber (cm -1 ) Explanation 2850 CH 3 symmetric and asymmetric stretch 2800 and 2700 Aldehyde C-H stretch consists of a pair of signals 1720 Aliphatic C=O stretching 1480 Aliphatic CH 2 bending (scissoring) 1320 Aliphatic CH 3 bending (symmetrical) 720 Aliphatic CH 2 rocking Table 21: Nonanal IR frequencies.

29 Ketones Ketones show strong C=O carbonyl stretching signals between 1780 and 1615 cm -1 (Figure 31). Aromatic and conjugated ketone systems will exhibit lower carbonyl frequencies than their aliphatic counterparts. The infrared spectra of 1,2-diketones will show one strong carbonyl signal near 1716 cm -1. The infrared spectra of 1,3-diketones are usually complex; this is because, 1,3-diketones typically undergo keto-enol tautomerism (Figure 30). Figure 30: Keto-enol tautomerism in 1,3-diketones. Note that for these compounds not only carbonyl but alcohol and alkene frequencies can be detected in the infrared spectrum (s) Aliphatic C=O stretching (s) Aromatic C=O stretching Table 22: Important frequencies in ketones. In liquid or solid state spectra C=O stretching frequencies will be lowered by ~10-20 cm -1, while in vapor phase spectra they will be raised by ~20 cm -1. i Figure 31: The infrared spectrum of acetophenone.

30 29 Wavenumber (cm -1 ) Explanation 3000 Aromatic C-H stretching (sp 2 absorption) 2850 CH 3 symmetric and asymmetric stretch Aromatic overtone/combination bands 1650 Aromatic C=O stretching 1600 Aromatic C=C stretching 1280 Aromatic =C-H in-plane bending Mono substituted aromatic ring Table 23: Acetophenone IR frequencies. α,β-unsaturated Often two bands α,β-, α,β -Unsaturated and diaryl Cyclopropyl Six-ring ketones and larger Similar to the corresponding open chain ketone Five-ring ketones Four-ring ketones ~1780 α-chloro or α-bromo α,α -Dichloro or α,α -Dibromo Affected by conformation; when halogen is in the same plane as C=O higher frequencies are observed Asymmetrical stretching of both C=O groups 1,2-Diketones s-trans (i.e. open chains) ,2-Diketones s-cis, six-ring 1760 and ,2-Diketones s-cis, five-ring 1775 and 1760 Enolised 1,3-diketones 1650 and 1615 C=O lowered by H bonding and C=C Table 24: Ketone carbonyl absorption bands C=O (all bands are strong). Figure 31b: Ketone compounds.

31 Carboxylic Acid Carboxylic acids exhibit a very strong carbonyl signal from cm -1. The exact position of this band depends on whether the carboxylic acid is saturated, unsaturated, dimerized, or has internal H-bonding (Figure 32). Centered near 3000 cm -1, the O-H stretch of carboxylic acids appears as a broad band between 3400 and 2400 cm -1. The reason the O-H band is broad is that carboxylic acids usually exist as H-bonded dimers. The broad O-H stretch often obscures C-H vibrations occurring in the same region The presence of a broad O-H band plus a strong carbonyl frequency, almost certainly confirms the analyte is a carboxylic acid (s) Carboxylic acid O-H stretch (broad peak) (s) Saturated (s) α,β-unsaturated (s) Aryl (s) α-halo C=O stretching (s) and (s) C-O-H bending C-O stretching Table 25: Important frequencies in carboxylic acids. i Figure 32: The infrared spectrum of benzoic acid.

32 31 Wavenumber (cm -1 ) Explanation 3100 Aromatic C-H stretching (sp 2 absorption) 3000 O-H stretch from carboxylic acid Aromatic overtone/combination bands 1690 C=O stretch from carboxylic acid 1600 Aromatic C=C stretching 1420 C-O-H bending 1300 C-O stretching Mono substituted aromatic ring Table 26: Benzoic acid IR frequencies.

33 Esters In esters, the C-O stretch appears as two or more bands (usually one stronger than the others) in the range cm -1 (Figure 33). Cyclic esters, known as lactones, will exhibit lower carbonyl frequencies than their non-cyclic counterparts. The ring size effect in esters is important whenever the size of the ring is equal to or lower than six membered (the smaller the ring size, the higher the carbonyl frequency) (s) Aliphatic C=O stretching (s) Aromatic and α,β-unsaturated C=O stretching (s) Usually two strong bands Table 27: Important frequencies in esters. i Figure 33: The infrared spectrum of hexyl butyrate. Wavenumber (cm -1 ) Explanation 3500 Carbonyl overtone 2850 CH 3 symmetric and asymmetric stretch 1740 C=O stretch from ester 1360 Aliphatic CH 3 bending (symmetric) Aliphatic C-O stretching 720 Aliphatic CH 2 bending (scissoring) Table 28: Hexyl butyrate IR frequencies.

34 (s) Aryl and vinyl esters (s) Esters with electronegative α-substituents (e.g. Cl) α-keto esters (s) Six-ring and larger lactones Similar values to the corresponding open chain esters Five-ring lactone (s) α,β-unsaturated five-ring lactone (s) Two bands seen in the presence of αc-h β,γ-unsaturated five-ring lactone ~1800(s) Four-ring lactone ~1820(s) β-keto ester in H-bonding enol form ~1650(s) Table 29: Ester stretching frequencies. Figure 33b: Ester compounds.

35 Amides Amides exhibit a strong carbonyl stretching frequency in the region cm -1 (Figure 34). Amides give two bands which can be attributed to forms 1 and 2. The carbonyl region of many amide compounds will also exhibit two bands. Hydrogen bonding lowers and broadens N-H stretching frequencies, but to a lesser extent than is seen for O-H functional groups. 3500(m) 3400(m) N-H stretch primary amide (two signals) (m) N-H stretch secondary amide (two bands. Only one band with lactams) (m) N-H bending primary amide (w) N-H bending secondary amide N-H wagging (s) C=O stretching C-N stretch Table 30: Important frequencies in amides. i Figure 34: The infrared spectrum of N-methylacetamide.

36 35 Wavenumber (cm -1 ) Explanation 3280 N-H stretch secondary amine 3100 Overtone signal located in the region cm CH 3 symmetric and asymmetric stretch 1680 C=O amide stretch 1560 N-H bending secondary amide 1530 C-N stretch N-H wagging Table 31: N-methylacetamide IR frequencies.

37 Anhydrides Anhydrides exhibit two strong carbonyl signals in the cm -1 region. These correspond to the symmetric and asymmetric stretch (Figure 35). The two carbonyl bands are usually separated by ~60 cm -1, with the higher frequency band being more intense in acyclic anhydrides and the lower frequency band is more intense in cyclic anhydrides. One or two strong bands may be observed due to the C-O stretching frequency in the cm -1 region (s) (s) (s) (s) (s) (s) (s) C=O stretch Two bands usually separated by ~60 cm -1 Aryl and α,β-unsaturated Saturated five-ring C-O stretch One or two strong bands Table 32: Important frequencies in anhydrides. i Figure 35: The infrared spectrum of propionic anhydride. Wavenumber (cm -1 ) Explanation 2900 CH 3 symmetric and asymmetric stretch 1819 Anhydride C=O symmetric stretch 1750 Anhydride C=O asymmetric stretch 1100 Anhydride C-O stretch Table 33: Propionic anhydride IR frequencies.

38 Acid Chlorides A weak overtone signal located in the region cm -1 is sometimes detectable. In some aromatic acid chlorides, a strong band on the lower side of the carbonyl C=O stretching will be present, resulting in the carbonyl appearing as a doublet. This phenomenon is known as a Fermi resonance (named after the great Italian physicist Enrico Fermi, who first explained the phenomenon) (s) C=O stretching saturated (Acid fluorides higher, bromides and iodides lower) (s) C=O stretching aryl and α,β-unsaturated (s) C-Cl stretch Table 34: Important frequencies in acid chlorides. i Figure 36: The infrared spectrum of benzoyl chloride. Wavenumber (cm -1 ) Explanation 3000 Aromatic C-H stretching (sp 2 absorption) 1780 C=O stretching (conjugated chlorides) 1700 The second carbonyl band exhibited by benzoyl chloride is attributable to Fermi Resonance (named after the Italian physicist Enrico Fermi who first explained the phenomenon) 1600 Aromatic C=C stretch Mono substituted aromatic ring C-Cl stretch Table 35: Benzoyl chloride IR frequencies.

39 Fermi Resonance A Fermi resonance is the shifting of the energies and intensities of absorption bands in an infrared or Raman spectrum, and is a consequence of quantum mechanical mixing. Two criteria must be fulfilled for Fermi Resonance to occur: 1. The two vibrations must have the same symmetries 2. The transitions have almost the same energy Fermi resonance most often occurs between normal and overtone modes if they are approximately coincident in energy. Fermi resonance results in two effects: 1. The high energy mode is shifted to higher energy, while the low energy mode is shifted to lower energy 2. An increase in intensity will be seen for the weaker band, and the more intense band will decrease in energy The two transitions can be thought of as a linear combination of the parent modes. Figure 37: Example of intensity and frequency shifts due to Fermi resonance. The top bands represent two fundamental vibrations without Fermi resonance, and the bottom bands show the change in bands as a result (left). The two energy levels are split such that one increases and the other decreases in energy, known as a Fermi doublet and they move away from each other.

40 39 In the case of saturated acid chlorides, i.e. acetyl chloride, strong carbonyl stretching frequencies are present at cm -1 (Figure 38). When the carbonyl group is conjugated to an aromatic system, as in benzoyl chloride, a second (usually less intense) carbonyl stretching frequency will appear at ~1730 cm -1 (Figure 38). The occurrence of a second stretching frequency is attributable to Fermi resonance involving the fundamental C=O stretching frequency (~1780 cm -1 ) and the first overtone of an intense aryl C-H bending mode (~900 cm -1 ). Figure 38: IR spectrum of acetyl chloride (top) and benzoyl chloride (bottom).

41 Stretching Frequencies Carbonyl Imides Cyclic six-ring Cyclic five-ring ~1710 and 1700(s) ~1770 and 1700(s) +15 cm -1 shift with α,βunsaturation Ureas RNHCONHR Six-ring Five-ring Urethanes Thioesters & Acids ~1660(s) ~1640(s) ~1720(s) (s) (s) Non- or mono-substitution on N will give amide II band ~-25 cm -1 shift with α,βunsaturation RCOSH ~1720(s) RCOS-alkyl ~1690(s) RCOS-aryl ~1710(s) Table 36: IR frequencies of carbonyl containing compounds. Carbonyl absorption frequencies are always strong. Figure 39: Carbonyl containing compounds.

42 Carbonates 41 ~1780(s) ~1740(s) ~1785(s) ~1820(s) Cyclic five-ring ~1645(s) ~1715(s) Table 37: IR frequencies of carbonyl containing compounds. Carbonyl absorption frequencies are always strong.

43 Nitrogen (m) N-H stretching (lower when H-bonded) Large variations in intensity and (v) close proximity to C=C stretching which makes α,β-unsaturated (v) identification difficult Conjugated cyclic systems (v) Table 38: IR frequencies of imines, oximes etc (v)(m) Very weak or inactive in IR Table 39: IR frequencies of azo compounds. Symmetric and asymmetric stretch Nitrates Nitramines (s) (s) (s) (s) (s) (2) (s) (s) (s) ~30 cm -1 lower when conjugated. Two bands due to symmetrical and asymmetrical NO stretch Saturated aryl Two bands (s) (s) Aromatic Aliphatic (very strong) Table 40: IR frequencies of nitro, nitroso etc. Figure 40: Imine compounds.

44 Sulfur (w) SH stretch (s) C=S stretch ~ (s) (s) N-H stretch Amide II Amide I ~1225 ~ ~1050 ~ (s) (s) (s) (s) (s) (s) SO 2 O (s) S F Table 41: IR frequencies of sulfur containing compounds.

45 Phosphorus, Boron, and Halogen P-H (s) Sharp P-Ph 1440(s) Sharp P-O-alkyl (s) P-O-aryl (s) P=O (s) P=S P-O-P Broad H-bonded O-H (s) p-f Table 42: IR frequencies of phosphorus containing compounds. P=O stretch B-H (s) B-O (vs) B-N (vs) B-C (s) Table 43: Boron containing compounds. C-F (s) Sharp Weaker C-Cl (s) C-Br C-I Inorganic (s) ~500(s) Table 44: Halogen containing compounds. Ammonium (s) + NH 3 Cyanide, thiocyanate, cyanate (s) CN -, SCN -, OCN - Carbonate (s) 2- CO 3 Sulfate (s) 2- SO 4 Nitrate (s) NO 3- Nitrite (s) NO 2- Phosphates (s) 3- PO 4 Table 45: IR frequencies of inorganic ions.

46 References 1. John A. Dean. Lange s Handbook of Chemistry Section 7.5. Fifteenth Edition. United States of America. McGraw Hill Dudley H. Williams and Ian Fleming Spectroscopic Methods in Organic Chemistry Chapter 2. McGraw Hill

47 46

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