Substituent Effects. 7. Phenyl Derivatives. When Is a Fluorine a π-Donor?

Journal of Organic Chemistry

Volumn 63, Issue 11, 1998, Pages 3722-3730

  Wiberg, Kenneth B ^a   Rablen, Paul R ^b  

^a YALE UNIVERSITY   (United States)

^b SWARTHMORE COLLEGE   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000812055     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo980463b     Document Type: Article

References (28)

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12. Curtiss, L. A.; Raghavachari, K.; Trucks, G. W.; Pople, J. A. J. Chem. Phys. 1991, 94, 7221. Curtiss, L. A.; Carpenter, J. E.; Raghavachari, K.; Pople, J. A. J. Chem. Phys. 1992, 96, 9030.
13. Curtiss, L. A.; Raghavachari, K.; Trucks, G. W.; Pople, J. A. J. Chem. Phys. 1991, 94, 7221. Curtiss, L. A.; Carpenter, J. E.; Raghavachari, K.; Pople, J. A. J. Chem. Phys. 1992, 96, 9030.
14. Wiberg, K. B.; Rablen, P. R. J. Am. Chem. Soc. 1993, 115, 614.
15. With aniline, the inversion barrier is smaller than the rotational barrier (Lister, D. G.; Tyler, J. K. J. Chem. Soc., Chem. Commun. 1966, 152. Lister, D. G.; Tyler, J. K.; Hog, J. H.; Larsen, N. W. J. Mol. Struct. 1974, 23, 253). The experimental rotational barrier for phenol is 3.3 kcal/mol (Forest, H.; Dailey, B. P. J. Chem. Phys. 1966, 45, 1736. Pedersen, T.; Larsen, N. W.; Nygaard, L. J. Mol. Struct. 1969, 4, 59).
16. With aniline, the inversion barrier is smaller than the rotational barrier (Lister, D. G.; Tyler, J. K. J. Chem. Soc., Chem. Commun. 1966, 152. Lister, D. G.; Tyler, J. K.; Hog, J. H.; Larsen, N. W. J. Mol. Struct. 1974, 23, 253). The experimental rotational barrier for phenol is 3.3 kcal/mol (Forest, H.; Dailey, B. P. J. Chem. Phys. 1966, 45, 1736. Pedersen, T.; Larsen, N. W.; Nygaard, L. J. Mol. Struct. 1969, 4, 59).
17. With aniline, the inversion barrier is smaller than the rotational barrier (Lister, D. G.; Tyler, J. K. J. Chem. Soc., Chem. Commun. 1966, 152. Lister, D. G.; Tyler, J. K.; Hog, J. H.; Larsen, N. W. J. Mol. Struct. 1974, 23, 253). The experimental rotational barrier for phenol is 3.3 kcal/mol (Forest, H.; Dailey, B. P. J. Chem. Phys. 1966, 45, 1736. Pedersen, T.; Larsen, N. W.; Nygaard, L. J. Mol. Struct. 1969, 4, 59).
18. With aniline, the inversion barrier is smaller than the rotational barrier (Lister, D. G.; Tyler, J. K. J. Chem. Soc., Chem. Commun. 1966, 152. Lister, D. G.; Tyler, J. K.; Hog, J. H.; Larsen, N. W. J. Mol. Struct. 1974, 23, 253). The experimental rotational barrier for phenol is 3.3 kcal/mol (Forest, H.; Dailey, B. P. J. Chem. Phys. 1966, 45, 1736. Pedersen, T.; Larsen, N. W.; Nygaard, L. J. Mol. Struct. 1969, 4, 59).
19. The structure of thiophenol does not appear to have been precisely determined. The available data suggest that it is nonplanar (Lunazzi, L.; Bellomo, P.; Veracini, C. A.; Amanzi, A. J. Chem. Soc., Perkin Trans. 2 1979, 559). Benzene-1,4-dithiol has been found to be nonplanar (Portalone, G.; Domenicano, A.; Schultz, G.; Hargittai, I. J. Mol. Struct. 1989, 186, 185).
20. The structure of thiophenol does not appear to have been precisely determined. The available data suggest that it is nonplanar (Lunazzi, L.; Bellomo, P.; Veracini, C. A.; Amanzi, A. J. Chem. Soc., Perkin Trans. 2 1979, 559). Benzene-1,4-dithiol has been found to be nonplanar (Portalone, G.; Domenicano, A.; Schultz, G.; Hargittai, I. J. Mol. Struct. 1989, 186, 185).
21. Wiberg, K. B.; Ochterski, J. J. Comput. Chem. 1997, 18, 108.
22. 2 = 0.974.
23. Pedley, J. B. Thermochemical Data and Structures of Organic Compounds; Thermodynamics Research Center: College Station, TX, 1994; Vol. 1.
24. Davico, G. E.; Bierbaum, V. M.; DePuy, C. H.; Ellison, G. B.; Squires, R. R. J. Am. Chem. Soc. 1995, 117, 2590.
25. Pauling, L. The Nature of the Chemical Bond; Cornell University.
26. The integrations were extrapolated to a zero value of ρ as previously described (ref 5).
27. Gaussian 94: Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Gill, P. M. W.; Johnson, B. G.; Robb, M. A.; Cheeseman, J. R.; Keith, T. A.; Petersson, G. A.; Montgomery, J. A.; Raghavachari, K.; Al-Laham, M. A.; Zakrzewski, V. G.; Ortiz, J. V.; Foresman, J. B.; Cioslowski, J.; Stefanov, B. B.; Nanayakkara, A.; Challacombe, M.; Peng, C. Y.; Ayala, P. Y.; Chen, W.; Wong, M. W.; Andres, J. L.; Replogle, S. S.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Binkley, J. S.; Defrees, D. J.; Baker, J.; Stewart, J. P.; Head-Gordon, M.; Gonzalez, C.; Pople, J. A. Gaussian, Inc., Pittsburgh, PA, 1994.
28. Rablen P. R. Ph.D. Thesis, Yale University, 1994.