The role of electrostatic effects in organic chemistry

Journal of Chemical Education

Volumn 73, Issue 11, 1996, Pages 1089-1095

  Wiberg, Kenneth B ^a  

^a YALE UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000699233     PISSN: 00219584     EISSN: None     Source Type: Journal    
DOI: 10.1021/ed073p1089     Document Type: Article

References (68)

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7. It should be noted that some authors have stressed the importance of charge distributions in determining properties of compounds: see Sanderson, R. T. Polar Covalence; Academic: New York, 1983; Fliszar, S. Charge Distributions and Chemical Effects, Springer: New York, 1983; Luo, Y.-R.; Benson, S. W. J. Am. Chem. Soc. 1989, 111, 2480.
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26. In solution, the experimental barrier in acetamide is 17 kcal/mol (Drakenberg, T. Tetrahedron Lett. 1972, 13, 1743), but it is higher in solution than in the gas phase (Stewart, W. E.; Siddall, T. H., III Chem. Rev. 1970, 70, 517). For a recent study of the effect of solvents on the rotational barrier in amides see Wiberg, K. B.; Rablen, P. R.; Rush, D. J. Am. Chem. Soc. 1995, 117, 4261.
27. In solution, the experimental barrier in acetamide is 17 kcal/mol (Drakenberg, T. Tetrahedron Lett. 1972, 13, 1743), but it is higher in solution than in the gas phase (Stewart, W. E.; Siddall, T. H., III Chem. Rev. 1970, 70, 517). For a recent study of the effect of solvents on the rotational barrier in amides see Wiberg, K. B.; Rablen, P. R.; Rush, D. J. Am. Chem. Soc. 1995, 117, 4261.
28. Wiberg, K. B.; Hadad, C. M.; Rablen, P. R.; Cioslowski, J. J. Am. Chem. Soc. 1992, 114, 8644.
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30. The origin of the increased acidity of acetic acid over ethanol has been the subject of much discussion and some controversy. The original observation suggesting that electronegativity of oxygen was the dominent factor was made by Siggel, M. R.; Thomas, T. D. J. Am. Chem. Soc. 1986, 108, 4360. Subsequent work supporting this proposal: Wiberg, K. B.; Laidig, K. E. J. Am. Chem. Soc. 1988, 110, 1872; Siggel, M. R.; Streitwieser, A., Jr.; Thomas, T. D. J. Am. Chem. Soc. 1988, 110, 8022; Thomas, T. D.; Siggel, M. E. F.; Streitwieser, A., Jr. J. Mol. Struct. 1988, 108, 308; Wiberg, K. B.; Breneman, C. M.; LePage, T. J. J. Am. Chem. Soc. 1990, 112, 61; Ji, D.; Thomas, T. D. J. Phys. Chem. 1994, 98, 4301. For a dissenting view, see Dewar, M. J. S.; Krull, K. L. J. Chem. Soc. Chem. Commun. 1990, 333; Exner, O. J. Org. Chem. 1988, 53, 1810. For more recent discussions see Hibert, P. C.; Byrman, C. P. J. Am. Chem. Soc. 1995, 177, 9875; and Wiberg, K. B.; Ochterski, J.; Streitwieser, A. J. Am. Chem. Soc. 1996, 188, 8291.
31. The origin of the increased acidity of acetic acid over ethanol has been the subject of much discussion and some controversy. The original observation suggesting that electronegativity of oxygen was the dominent factor was made by Siggel, M. R.; Thomas, T. D. J. Am. Chem. Soc. 1986, 108, 4360. Subsequent work supporting this proposal: Wiberg, K. B.; Laidig, K. E. J. Am. Chem. Soc. 1988, 110, 1872; Siggel, M. R.; Streitwieser, A., Jr.; Thomas, T. D. J. Am. Chem. Soc. 1988, 110, 8022; Thomas, T. D.; Siggel, M. E. F.; Streitwieser, A., Jr. J. Mol. Struct. 1988, 108, 308; Wiberg, K. B.; Breneman, C. M.; LePage, T. J. J. Am. Chem. Soc. 1990, 112, 61; Ji, D.; Thomas, T. D. J. Phys. Chem. 1994, 98, 4301. For a dissenting view, see Dewar, M. J. S.; Krull, K. L. J. Chem. Soc. Chem. Commun. 1990, 333; Exner, O. J. Org. Chem. 1988, 53, 1810. For more recent discussions see Hibert, P. C.; Byrman, C. P. J. Am. Chem. Soc. 1995, 177, 9875; and Wiberg, K. B.; Ochterski, J.; Streitwieser, A. J. Am. Chem. Soc. 1996, 188, 8291.
32. The origin of the increased acidity of acetic acid over ethanol has been the subject of much discussion and some controversy. The original observation suggesting that electronegativity of oxygen was the dominent factor was made by Siggel, M. R.; Thomas, T. D. J. Am. Chem. Soc. 1986, 108, 4360. Subsequent work supporting this proposal: Wiberg, K. B.; Laidig, K. E. J. Am. Chem. Soc. 1988, 110, 1872; Siggel, M. R.; Streitwieser, A., Jr.; Thomas, T. D. J. Am. Chem. Soc. 1988, 110, 8022; Thomas, T. D.; Siggel, M. E. F.; Streitwieser, A., Jr. J. Mol. Struct. 1988, 108, 308; Wiberg, K. B.; Breneman, C. M.; LePage, T. J. J. Am. Chem. Soc. 1990, 112, 61; Ji, D.; Thomas, T. D. J. Phys. Chem. 1994, 98, 4301. For a dissenting view, see Dewar, M. J. S.; Krull, K. L. J. Chem. Soc. Chem. Commun. 1990, 333; Exner, O. J. Org. Chem. 1988, 53, 1810. For more recent discussions see Hibert, P. C.; Byrman, C. P. J. Am. Chem. Soc. 1995, 177, 9875; and Wiberg, K. B.; Ochterski, J.; Streitwieser, A. J. Am. Chem. Soc. 1996, 188, 8291.
33. The origin of the increased acidity of acetic acid over ethanol has been the subject of much discussion and some controversy. The original observation suggesting that electronegativity of oxygen was the dominent factor was made by Siggel, M. R.; Thomas, T. D. J. Am. Chem. Soc. 1986, 108, 4360. Subsequent work supporting this proposal: Wiberg, K. B.; Laidig, K. E. J. Am. Chem. Soc. 1988, 110, 1872; Siggel, M. R.; Streitwieser, A., Jr.; Thomas, T. D. J. Am. Chem. Soc. 1988, 110, 8022; Thomas, T. D.; Siggel, M. E. F.; Streitwieser, A., Jr. J. Mol. Struct. 1988, 108, 308; Wiberg, K. B.; Breneman, C. M.; LePage, T. J. J. Am. Chem. Soc. 1990, 112, 61; Ji, D.; Thomas, T. D. J. Phys. Chem. 1994, 98, 4301. For a dissenting view, see Dewar, M. J. S.; Krull, K. L. J. Chem. Soc. Chem. Commun. 1990, 333; Exner, O. J. Org. Chem. 1988, 53, 1810. For more recent discussions see Hibert, P. C.; Byrman, C. P. J. Am. Chem. Soc. 1995, 177, 9875; and Wiberg, K. B.; Ochterski, J.; Streitwieser, A. J. Am. Chem. Soc. 1996, 188, 8291.
34. The origin of the increased acidity of acetic acid over ethanol has been the subject of much discussion and some controversy. The original observation suggesting that electronegativity of oxygen was the dominent factor was made by Siggel, M. R.; Thomas, T. D. J. Am. Chem. Soc. 1986, 108, 4360. Subsequent work supporting this proposal: Wiberg, K. B.; Laidig, K. E. J. Am. Chem. Soc. 1988, 110, 1872; Siggel, M. R.; Streitwieser, A., Jr.; Thomas, T. D. J. Am. Chem. Soc. 1988, 110, 8022; Thomas, T. D.; Siggel, M. E. F.; Streitwieser, A., Jr. J. Mol. Struct. 1988, 108, 308; Wiberg, K. B.; Breneman, C. M.; LePage, T. J. J. Am. Chem. Soc. 1990, 112, 61; Ji, D.; Thomas, T. D. J. Phys. Chem. 1994, 98, 4301. For a dissenting view, see Dewar, M. J. S.; Krull, K. L. J. Chem. Soc. Chem. Commun. 1990, 333; Exner, O. J. Org. Chem. 1988, 53, 1810. For more recent discussions see Hibert, P. C.; Byrman, C. P. J. Am. Chem. Soc. 1995, 177, 9875; and Wiberg, K. B.; Ochterski, J.; Streitwieser, A. J. Am. Chem. Soc. 1996, 188, 8291.
35. The origin of the increased acidity of acetic acid over ethanol has been the subject of much discussion and some controversy. The original observation suggesting that electronegativity of oxygen was the dominent factor was made by Siggel, M. R.; Thomas, T. D. J. Am. Chem. Soc. 1986, 108, 4360. Subsequent work supporting this proposal: Wiberg, K. B.; Laidig, K. E. J. Am. Chem. Soc. 1988, 110, 1872; Siggel, M. R.; Streitwieser, A., Jr.; Thomas, T. D. J. Am. Chem. Soc. 1988, 110, 8022; Thomas, T. D.; Siggel, M. E. F.; Streitwieser, A., Jr. J. Mol. Struct. 1988, 108, 308; Wiberg, K. B.; Breneman, C. M.; LePage, T. J. J. Am. Chem. Soc. 1990, 112, 61; Ji, D.; Thomas, T. D. J. Phys. Chem. 1994, 98, 4301. For a dissenting view, see Dewar, M. J. S.; Krull, K. L. J. Chem. Soc. Chem. Commun. 1990, 333; Exner, O. J. Org. Chem. 1988, 53, 1810. For more recent discussions see Hibert, P. C.; Byrman, C. P. J. Am. Chem. Soc. 1995, 177, 9875; and Wiberg, K. B.; Ochterski, J.; Streitwieser, A. J. Am. Chem. Soc. 1996, 188, 8291.
36. The origin of the increased acidity of acetic acid over ethanol has been the subject of much discussion and some controversy. The original observation suggesting that electronegativity of oxygen was the dominent factor was made by Siggel, M. R.; Thomas, T. D. J. Am. Chem. Soc. 1986, 108, 4360. Subsequent work supporting this proposal: Wiberg, K. B.; Laidig, K. E. J. Am. Chem. Soc. 1988, 110, 1872; Siggel, M. R.; Streitwieser, A., Jr.; Thomas, T. D. J. Am. Chem. Soc. 1988, 110, 8022; Thomas, T. D.; Siggel, M. E. F.; Streitwieser, A., Jr. J. Mol. Struct. 1988, 108, 308; Wiberg, K. B.; Breneman, C. M.; LePage, T. J. J. Am. Chem. Soc. 1990, 112, 61; Ji, D.; Thomas, T. D. J. Phys. Chem. 1994, 98, 4301. For a dissenting view, see Dewar, M. J. S.; Krull, K. L. J. Chem. Soc. Chem. Commun. 1990, 333; Exner, O. J. Org. Chem. 1988, 53, 1810. For more recent discussions see Hibert, P. C.; Byrman, C. P. J. Am. Chem. Soc. 1995, 177, 9875; and Wiberg, K. B.; Ochterski, J.; Streitwieser, A. J. Am. Chem. Soc. 1996, 188, 8291.
37. The origin of the increased acidity of acetic acid over ethanol has been the subject of much discussion and some controversy. The original observation suggesting that electronegativity of oxygen was the dominent factor was made by Siggel, M. R.; Thomas, T. D. J. Am. Chem. Soc. 1986, 108, 4360. Subsequent work supporting this proposal: Wiberg, K. B.; Laidig, K. E. J. Am. Chem. Soc. 1988, 110, 1872; Siggel, M. R.; Streitwieser, A., Jr.; Thomas, T. D. J. Am. Chem. Soc. 1988, 110, 8022; Thomas, T. D.; Siggel, M. E. F.; Streitwieser, A., Jr. J. Mol. Struct. 1988, 108, 308; Wiberg, K. B.; Breneman, C. M.; LePage, T. J. J. Am. Chem. Soc. 1990, 112, 61; Ji, D.; Thomas, T. D. J. Phys. Chem. 1994, 98, 4301. For a dissenting view, see Dewar, M. J. S.; Krull, K. L. J. Chem. Soc. Chem. Commun. 1990, 333; Exner, O. J. Org. Chem. 1988, 53, 1810. For more recent discussions see Hibert, P. C.; Byrman, C. P. J. Am. Chem. Soc. 1995, 177, 9875; and Wiberg, K. B.; Ochterski, J.; Streitwieser, A. J. Am. Chem. Soc. 1996, 188, 8291.
38. The origin of the increased acidity of acetic acid over ethanol has been the subject of much discussion and some controversy. The original observation suggesting that electronegativity of oxygen was the dominent factor was made by Siggel, M. R.; Thomas, T. D. J. Am. Chem. Soc. 1986, 108, 4360. Subsequent work supporting this proposal: Wiberg, K. B.; Laidig, K. E. J. Am. Chem. Soc. 1988, 110, 1872; Siggel, M. R.; Streitwieser, A., Jr.; Thomas, T. D. J. Am. Chem. Soc. 1988, 110, 8022; Thomas, T. D.; Siggel, M. E. F.; Streitwieser, A., Jr. J. Mol. Struct. 1988, 108, 308; Wiberg, K. B.; Breneman, C. M.; LePage, T. J. J. Am. Chem. Soc. 1990, 112, 61; Ji, D.; Thomas, T. D. J. Phys. Chem. 1994, 98, 4301. For a dissenting view, see Dewar, M. J. S.; Krull, K. L. J. Chem. Soc. Chem. Commun. 1990, 333; Exner, O. J. Org. Chem. 1988, 53, 1810. For more recent discussions see Hibert, P. C.; Byrman, C. P. J. Am. Chem. Soc. 1995, 177, 9875; and Wiberg, K. B.; Ochterski, J.; Streitwieser, A. J. Am. Chem. Soc. 1996, 188, 8291.
39. The origin of the increased acidity of acetic acid over ethanol has been the subject of much discussion and some controversy. The original observation suggesting that electronegativity of oxygen was the dominent factor was made by Siggel, M. R.; Thomas, T. D. J. Am. Chem. Soc. 1986, 108, 4360. Subsequent work supporting this proposal: Wiberg, K. B.; Laidig, K. E. J. Am. Chem. Soc. 1988, 110, 1872; Siggel, M. R.; Streitwieser, A., Jr.; Thomas, T. D. J. Am. Chem. Soc. 1988, 110, 8022; Thomas, T. D.; Siggel, M. E. F.; Streitwieser, A., Jr. J. Mol. Struct. 1988, 108, 308; Wiberg, K. B.; Breneman, C. M.; LePage, T. J. J. Am. Chem. Soc. 1990, 112, 61; Ji, D.; Thomas, T. D. J. Phys. Chem. 1994, 98, 4301. For a dissenting view, see Dewar, M. J. S.; Krull, K. L. J. Chem. Soc. Chem. Commun. 1990, 333; Exner, O. J. Org. Chem. 1988, 53, 1810. For more recent discussions see Hibert, P. C.; Byrman, C. P. J. Am. Chem. Soc. 1995, 177, 9875; and Wiberg, K. B.; Ochterski, J.; Streitwieser, A. J. Am. Chem. Soc. 1996, 188, 8291.
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