α-C-H bond dissociation energies of some tertiary amines

Journal of Organic Chemistry

Volumn 64, Issue 2, 1999, Pages 427-431

  Dombrowski, G W ^a   Dinnocenzo, J P ^a   Farid, S ^a   Goodman, J L ^a   Gould, I R ^a  

^a NONE

Author keywords

[No Author keywords available]

Indexed keywords

PHENYL GROUP; TERTIARY AMINE; VINYL DERIVATIVE;

ARTICLE; CALORIMETRY; CHEMICAL BOND; DISSOCIATION; ENERGY; STEREOCHEMISTRY;

EID: 0033593262     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo9813843     Document Type: Article

References (38)

1. Not included in the present discussion is work related to α-amino radical stabilization in captodatively substituted radicals. For leading references, see: Welle, F. M.; Beckhaus, H.-D.; Rüchardt, C. J. Org. Chem. 1997, 62, 552.
2. f(H•) = 52.1 kcal/mol (Lias, S. G.; Bartmess, J. E.; Liebman, J. F.; Holmes, J. L.; Levin, R. D.; Mallard, W. G. Gas-Phase Ion and Neutral Thermochemistry. Lide, D. R., Jr., Ed. J. Phys. Chem. Ref. Data 1988, 17, Suppl. No. 1).
3. f(H•) = 52.1 kcal/mol (Lias, S. G.; Bartmess, J. E.; Liebman, J. F.; Holmes, J. L.; Levin, R. D.; Mallard, W. G. Gas-Phase Ion and Neutral Thermochemistry. Lide, D. R., Jr., Ed. J. Phys. Chem. Ref. Data 1988, 17, Suppl. No. 1).
4. Berkowitz, J.; Ellison, G. B.; Gutman, D. J. Phys. Chem. 1994, 98, 2744.
5. Richey, H. G., Jr.; Shull, D. W. Tetrahedron Lett. 1976, 575.
6. (a) Griller, D.; Lossing, F. P. J. Am. Chem. Soc. 1981, 103, 1586.
7. (b) Burkey, T. J.; Castelhano, A. L.; Griller, D.; Lossing, F. P. J. Am. Chem. Soc. 1983, 105, 4701.
8. Goddard, J. D. Can. J. Chem. 1982, 60, 1250.
9. Grela, M. A.; Colussi, A. J. J. Phys. Chem. 1984, 88, 5995.
10. 3
11. Clark, K. B.; Wayner, D. D. M.; Demirdji, S. H.; Koch, T. H. J. Am. Chem. Soc. 1993, 115, 2447.
12. Wayner, D. D. M.; Clark, K. B.; Rauk, A.; Yu, D.; Armstrong, D. A. J. Am. Chem. Soc. 1997, 119, 8925.
13. Armstrong, D. A.; Rauk, A.; Yu, D. J. Am. Chem. Soc. 1993, 115, 666.
14. Ochterski, J. W.; Petersson, G. A.; Wiberg, K. B. J. Am. Chem. Soc. 1995, 117, 11299.
15. Dinnocenzo, J. P.; Banach, T. E. J. Am. Chem. Soc. 1989, 111, 8646.
16. (a) Braslavsky, S. E.; Heibel, G. E. Chem. Rev. 1992, 92, 1381.
17. (b) Goodman, J. L. In Energetics of Organic Free Radicals; Simões, J. A. M., Greenberg, A., Liebman, J. F., Eds.; Blackie: New York, 1996; Vol. 4, Chapter 5.
18. (a) Inbar, S.; Linschitz, H.; Cohen, S. G. J. Am. Chem. Soc. 1980, 102, 1419.
19. (b) Inbar, S.; Linschitz, H.; Cohen, S. G. J. Am. Chem. Soc. 1981, 103, 1048.
20. Arnaut, L. G.; Caldwell, R. A. J. Photochem. Photobiol. A: Chem. 1992, 65, 15.
21. Cambron, R. T.; Harris, J. M. J. Phys. Chem. 1993, 97, 13598.
22. Lucarini, M.; Pedrielli, P.; Pedulli, G. F.; Cabiddu, S.; Fattuoni, C. J. Org. Chem. 1996, 61, 9259.
23. (a) Miyasaka, H.; Monta, K.; Kamada, K.; Nagata, T.; Kiri, M.; Mataga, N. Bull. Chem. Soc. Jpn. 1991, 64, 3229.
24. (b) von Raumer, M.; Suppan, P.; Haselbach, E. Helv. Chim. Acta 1997, 80, 719.
25. If a small amount of triplet to singlet intersystem crossing occurs in the geminate ion radical pair, which is followed by rapid return electron transfer, the measured heat deposition will be slightly larger than that due solely to hydrogen atom transfer from the amine to triplet benzophenone. This leads to an apparent α-C-H amine BDE that is lower than the true value. A quantitative analysis shows that for quantum yields of benzhydrol radical formation ≥ 0.96, the maximum BDE correction would be +2.2 kcal/mol.
26. Murov, S. L.; Carmichael, I.; Hug, G. L. Handbook of Photochemistry, 2nd ed.; Marcel Dekker: New York, 1993.
27. Calculations performed using the Gaussian 94 suite of programs: Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Gill, P. M. W.; Johnson, B. G.; Robb, M. A.; Cheeseman, J. R.; Keith, T.; 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, E. 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 94, Revision C.3; Gaussian, Inc., Pittsburgh, PA, 1995.
28. 2 structure where the nitrogen lone pair is orthogonal to the plane of the aromatic ring, the sum of C-N-C bond angles is 341°.
29. 25
30. Ellison, G. B.; Davico, G. E.; Bierbaum, V. M.; DePuy, C. H. Int. J. Mass Spectrom. Ion Processes 1998, 156, 109.
31. (a) Lewis, F. D.; Ho, T.-I.; Simpson, J. T. J. Am. Chem. Soc. 1982, 104, 1924. For closely related work, see:
32. (b) Xu, W.; Mariano, P. S. J. Am. Chem. Soc. 1991, 113, 1431.
33. (c) Zhang, X.; Yeh, S.-R.; Hong, S.; Freccero, M.; Albini, A.; Falvey, D. E.; Mariano, P. S. J. Am. Chem. Soc. 1994, 116, 4211.
34. (d) Reference 30.
35. Giumanini, A. G.; Chiavari, G.; Musiani, M. M.; Rossi, P. Synthesis 1980, 9, 743.
36. Carnahan, F. L.; Hurd, C. D. J. Am. Chem. Soc. 1930, 52, 4581.
37. For a full description of the apparatus, see: Chen, L.; Farahat, M. S.; Gaillard, E. R.; Fand, S.; Whitten, D. G. J. Photochem. Photobiol. A 1996, 95, 21.
38. Griller, D.; Howard, J. A.; Marriott, P. R.; Scaiano, J. C. J. Am. Chem. Soc. 1981, 103, 619.