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Volumn 113, Issue 22, 2009, Pages 6275-6288

Intramolecular and intermolecular hydrogen bond formation by some ortho-substituted phenols: Some surprising results from an experimental and theoretical investigation

Author keywords

[No Author keywords available]

Indexed keywords

2-NITROPHENOL; [CARBONYL; DINITROPHENOL; FREQUENCY SHIFT; INTERMOLECULAR HYDROGEN BONDS; IR BANDS; IR SPECTRUM; METHOXY; METHOXYPHENOLS; O-H STRETCHING BANDS; OH GROUP; STRETCHING FREQUENCY; STRETCHING REGION; SUBSTITUTED PHENOL; THEORETICAL INVESTIGATIONS; THEORETICAL MODELING; WAVE NUMBERS;

EID: 66249085217     PISSN: 10895639     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp900876q     Document Type: Article
Times cited : (50)

References (73)
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    • Frisch, M. J, Trucks, G. W, Schlegel, H. B, Scuseria, G. E, Robb, M. A, Cheeseman, J. R, Montgomery, J. A, Jr, Vreven, T, Kudin, K. N, Burant, J. C, Millam, J. M, Iyengar, S. S, Tomasi, J. J, Barone, V, Mennucci, B, Cossi, M, Scalmani, G, Rega, N, Petersson, G. A, Nakatsuji, H, Hada, M, Ehara, M, Toyota, K, Fukuda, R, Hasegawa, J, Ishida, M, Nakajima, T, Honda, Y, Kitao, O, Nakai, H, Klene, M, Li, X, Knox, J. E, Hratchian, H. P, Cross, J. B, Adamo, C, Jaramillo, J, Gomperts, R, Stratmann, R. E, Yazyev, O, Austin, A. J, Cammi, R, Pomelli, C, Ochterski, J. W, Ayala, P. Y, Morokuma, K, Voth, A, Salvador, P, Dannenberg, J. J, Zakrzewski, V. G, Dapprich, S, Daniels, A. D, Strain, M. C, Farkas, O, Malick, D. K, Rabuck, A. D, Raghavachari, K, Foresman, J. B, Ortiz, J. V, Cui, Q, Baboul, A. G, Clifford, S, Cioslowski, J, Stefanov, B. B, Liu, G, Liashenko, A, Piskorz, P, Komaromi, I, Martin, R. L, Fox, D. J, Keith, T, Al-La
    • Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Montgomery, J. A., Jr.; Vreven, T.; Kudin, K. N.; Burant, J. C.; Millam, J. M.; Iyengar, S. S.; Tomasi, J. J.; Barone, V.; Mennucci, B.; Cossi, M.; Scalmani, G.; Rega, N.; Petersson, G. A.; Nakatsuji, H.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Klene, M.; Li, X.; Knox, J. E.; Hratchian, H. P.; Cross, J. B.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Ayala, P. Y.; Morokuma, K.; Voth, A.; Salvador, P.; Dannenberg, J. J.; Zakrzewski, V. G.; Dapprich, S.; Daniels, A. D.; Strain, M. C.; Farkas, O.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Ortiz, J. V.; Cui, Q.; Baboul, A. G.; Clifford, S.; Cioslowski, J.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M. W.; Gonzalez, C.; Pople, J. A. Gaussian 03, revision D.01; Gaussian, Inc.: Pittsburgh, PA, 2004.
  • 25
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    • 4 than in the gas phase (see: Ingold, K. U. Can. J. Chem. 1962, 40, 111 - 121), and in this low-dielectric solvent, relative energies are expected to be little changed compared to those in the gas phase. We therefore performed all calculations for isolated (nonsolvated) monomers and complexes.
    • 4 than in the gas phase (see: Ingold, K. U. Can. J. Chem. 1962, 40, 111 - 121), and in this low-dielectric solvent, relative energies are expected to be little changed compared to those in the gas phase. We therefore performed all calculations for isolated (nonsolvated) monomers and complexes.
  • 26
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    • +) = 9.24.
    • +) = 9.24.
  • 36
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    • (f) Chiş, V. Chem. Phys. 2004, 300, 1-11.
    • (2004) Chem. Phys , vol.300 , pp. 1-11
    • Chiş, V.1
  • 37
    • 66249102123 scopus 로고    scopus 로고
    • For an excellent review dealing mainly with intramolecular HBs, including those in ortho-substituted phenols
    • (g) For an excellent review dealing mainly with intramolecular HBs, including those in ortho-substituted phenols
  • 42
    • 66249115767 scopus 로고    scopus 로고
    • With one exception: 2-nitrophenol in nitrobenzene ref 20b
    • With one exception: 2-nitrophenol in nitrobenzene (ref 20b).
  • 43
    • 66249114773 scopus 로고    scopus 로고
    • The barrier to rotation of the OH group in phenol is 3.5 kcal/mol (ref 24).
    • The barrier to rotation of the OH group in phenol is 3.5 kcal/mol (ref 24).
  • 45
    • 66249090336 scopus 로고    scopus 로고
    • The sharp IR band at ca. 3100 cm-1 is due to a C3-H stretching mode, see ref 20f
    • 3-H stretching mode, see ref 20f.
  • 46
    • 66249107558 scopus 로고    scopus 로고
    • Intramolecular HB strengths were computed (ref 27), to a first approximation (ref 28), by taking the difference in enthalpy between the OH toward the ortho substituent H-bonded minimum enthalpy structure and the OH away minimum enthalpy structure following a 180° rotation of the OH group about the HO- C bond.
    • Intramolecular HB strengths were computed (ref 27), to a first approximation (ref 28), by taking the difference in enthalpy between the OH "toward the ortho substituent" H-bonded minimum enthalpy structure and the OH "away" minimum enthalpy structure following a 180° rotation of the OH group about the HO- C bond.
  • 47
    • 66249135440 scopus 로고    scopus 로고
    • By calculating the stabilization enthalpies for 2-XC6H 4OH (2,4-X2C6H4OH, C 6H6 → 2-XC6H5 (2,4-X 2C6H5, C6H5OH at the B971/6- 311++G(2d,2p) level of theory
    • 5OH at the B971/6- 311++G(2d,2p) level of theory.
  • 48
    • 66249120139 scopus 로고    scopus 로고
    • This is only a first approximation of the intramolecular HB strength because it incorporates enthalpies associated with resonance and inductive interactions between the OH group and the other substituents on the ring
    • This is only a first approximation of the intramolecular HB strength because it incorporates enthalpies associated with resonance and inductive interactions between the OH group and the other substituents on the ring.
  • 52
    • 66249127009 scopus 로고    scopus 로고
    • There would appear to be no 2,6-diacylphenols commercially available, and no easy synthesis of any of them was discovered in the literature. It was not possible, therefore, to look for a bifurcated hydrogen bond with DMSO using such a phenol.
    • There would appear to be no 2,6-diacylphenols commercially available, and no easy synthesis of any of them was discovered in the literature. It was not possible, therefore, to look for a bifurcated hydrogen bond with DMSO using such a phenol.
  • 53
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    • H value for nitrobenzene is 0.34, whereas the values for benzaldehyde and acetophenone are significantly greater, 0.42 and 0.51, respectively (ref 5).
    • H value for nitrobenzene is 0.34, whereas the values for benzaldehyde and acetophenone are significantly greater, 0.42 and 0.51, respectively (ref 5).
  • 58
  • 61
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    • In this paper, the band maxima for 2-acetyl, 2-formyl, and 2-nitro-phenol were reported to be 3050, 3150, and 3240 cm-1, respectively
    • -1, respectively.
  • 62
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    • The ortho- para method (ref 38) for estimating the enthalpy of this intramolecular HB from the difference in the calculated ground- state energies of 2-hydroxybenzaldehyde and 4-hydroxybenzaldehyde yielded values of 5.5 (CBS-QB3) and 5.6 (B3LYP/6-311+G(dp)) kcal/mol (ref 38b). As appears to be usual (ref 38), the ortho-para method gives lower (often much lower) intramolecular HB strengths than the cis- trans method we employed. There appears to be no compelling reason for choosing one method over the other. The ortho-para method yielded intramolecular HB strengths in 2-acetylphenol of 5.9 (CBS-QB3) and 6.3 (B3LYP/6-311+G(dp)) kcal/mol (ref 38b).
    • The "ortho- para method" (ref 38) for estimating the enthalpy of this intramolecular HB from the difference in the calculated ground- state energies of 2-hydroxybenzaldehyde and 4-hydroxybenzaldehyde yielded values of 5.5 (CBS-QB3) and 5.6 (B3LYP/6-311+G(dp)) kcal/mol (ref 38b). As appears to be usual (ref 38), the ortho-para method gives lower (often much lower) intramolecular HB strengths than the "cis- trans method" we employed. There appears to be no compelling reason for choosing one method over the other. The ortho-para method yielded intramolecular HB strengths in 2-acetylphenol of 5.9 (CBS-QB3) and 6.3 (B3LYP/6-311+G(dp)) kcal/mol (ref 38b).
  • 68
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    • Private communication
    • Mendenhall, G. D. Private communication.
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  • 69
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    • The ratio of the free phenol to the HB form was estimated (ref 39) to be 4:96, possibly from peak heights (our own peak height ratio is 5:95, Figure 9). However, this ratio overestimates the amount of the free phenol because HB bands are broader and generally of lower height than an equal quantity of a free phenol. A better measure of free phenol is given by the ratio of the integrated areas of the two bands, viz., 1.9:98.1. However, this ratio will underestimate the amount of free phenol because the integrated areas of the O-H stretching bands of phenols are greater when the phenol forms a HB than when it is free.
    • The ratio of the "free" phenol to the HB form was estimated (ref 39) to be 4:96, possibly from peak heights (our own peak height ratio is 5:95, Figure 9). However, this ratio overestimates the amount of the "free" phenol because HB bands are broader and generally of lower height than an equal quantity of a "free" phenol. A better measure of "free" phenol is given by the ratio of the integrated areas of the two bands, viz., 1.9:98.1. However, this ratio will underestimate the amount of "free" phenol because the integrated areas of the O-H stretching bands of phenols are greater when the phenol forms a HB than when it is "free".
  • 73
    • 66249091736 scopus 로고    scopus 로고
    • 4. A very similar equilibrium constant should apply to phenol (see text), indicating that for phenol in neat CCl4 about 20% of the hydroxyl groups will be hydrogen-bonded to a solvent molecule. This phenomenon is not distinguishable by IR, but it is in excellent agreement with earlier kinetic measurements (ref 3).
    • 4. A very similar equilibrium constant should apply to phenol (see text), indicating that for phenol in neat CCl4 about 20% of the hydroxyl groups will be hydrogen-bonded to a solvent molecule. This phenomenon is not distinguishable by IR, but it is in excellent agreement with earlier kinetic measurements (ref 3).


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