Revised structure for the diphenylaminyl radical: The importance of theory in the assignment of electronic transitions in Ph2Ẋ (X = CH, N) and PhẎ (Y = CH2, NH, O)

Journal of Physical Chemistry A

Volumn 106, Issue 48, 2002, Pages 11719-11725

  DiLabio, Gino A ^a   Litwinienko, Grzegorz ^a,c   Lin, Shuquiong ^a   Pratt, Derek A ^b   Ingold, K U ^a  

^a NATIONAL RESEARCH COUNCIL CANADA   (Canada)

^b VANDERBILT UNIVERSITY   (United States)

^c UNIVERSITY OF WARSAW   (Poland)

Author keywords

[No Author keywords available]

Indexed keywords

ABSORPTION SPECTROSCOPY; AROMATIC COMPOUNDS; ATOMS; CONFORMATIONS; ELECTRON TRANSITIONS; ELECTRONS; GROUND STATE; HYDROGEN; LASER APPLICATIONS; PHOTOLYSIS; PROBABILITY DENSITY FUNCTION; ULTRAVIOLET SPECTROSCOPY;

AROMATIC RINGS; DENSITY FUNCTIONAL THEORY; DIPHENYLAMINYL RADICAL;

FREE RADICALS;

EID: 0037028189     PISSN: 10895639     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp026279i     Document Type: Article

References (37)

1. Pratt, D. A.; DiLabio, G. A.; Valgimigli, L.; Pedulli, G. F.; Ingold, K. U. J. Am. Chem. Soc. 2002, 124, 1085-11092.
2. Leyva, E.; Platz, M. S.; Niu, B.; Wirz, J. J. Phys. Chem. 1987, 91, 2293-2298.
3. Wieland, H. Annalen 1911, 381, 200-216.
4. (b) Lewis, G. N.; Lipkin, D. J. Am. Chem. Soc. 1942, 64, 2801-2808.
5. (c) Wiersman, D. A.; Kommandeur, J. Mol. Phys. 1967, 13, 241-251.
6. (d) Shida, T.; Kira, A. J. Phys. Chem. 1969, 73, 4315-4320.
7. (e) Johnston, L. J.; Redmond, R. W. J. Phys. Chem. A 1997, 101, 4660-4665.
8. (a) Wieland, H. Chem. Ber. 1915, 48, 1078-1095.
9. (b) Neugebauer, F. A.; Fischer, P. H. H. Chem. Ber. 1965, 98, 844-850.
10. Bromberg, A.; Meisel, D. J. Phys. Chem. 1985, 89, 2507-2513.
11. Forrester, A. R.; Hay, J. M.; Thomson, F. H. Organic Chemistry of Stable Free Radicals; Academic: London, 1968; Chapter 3.
12. MacFaul, P. A.; Ingold, K. U.; Lusztyk, J. J. Org. Chem. 1996, 61, 1316-1321.
13. Lucarini, M.; Pedrielli, P.; Pedulli, G. F.; Valgimigli, L.; Gigmes, D.; Tordo, P. J. Am. Chem. Soc. 1999, 121, 11546-11553.
14. Dilabio, G. A.; Pratt, D. A.; LoFaro, A. D.; Wright, J. S. J. Phys. Chem. A 1999, 103, 1653-1661.
15. Shida, T.; Kira, A. Bull. Chem. Soc. Jpn. 1969, 42, 1197-1201.
16. Becke, A. D. J. Chem. Phys. 1993, 98, 5648-5652.
17. Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B 1988, 37, 785-789.
18. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Zakrzewski, V. G.; Montgonery, J. A., Jr.; Stratmann, R. E.; Burant, J. C.; Dapprich, S.; Millam, J. M.; Daniels, A. D.; Kudin, K. N.; Strain, M. C.; Farkas, O.; Tomasi, J.; Barone, V.; Cossi, M.; Cammi, R.; Mennucci, B.; Pomelli, C.; Adamo, C.; Clifford, S.; Ochterski, J.; Petersson, G. A.; Ayala, P. Y.; Cui, Q.; Morokuma, K.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Cioslowski, J.; Ortiz, J. V.; Baboul, A. G.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Gomperts, R.; 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.; Andres, J. L.; Gonzalez, C.; Head-Gordon, M.; Replogle, E. S.; Pople, J. A. Gaussian 98, revision A.9; Gaussian, Inc.: Pittsburgh, PA, 1998.
19. Stratmann, R. E.; Scuseria, G. E.; Frisch, M. J. J. Chem. Phys. 1998, 109, 8218-8224.
20. This transition can be envisaged as roughly corresponding to the promotion of an aromatic φ-electron into the N-2p SOMO, i.e., to the formation of a delocalized aromatic radical cation and a localized nitrogen anion.
21. Hirata, S.; Lee, T. J.; Head-Gordon, M. J. Chem. Phys. 1999, 111, 8904-8912.
22. ̇ is (are) preferentially conjugated with the lone pair on nitrogen rather than with the unpaired electron has been considered and rejected on the basis of substituents effects on the ESR spectra of ring-substituted diphenylaminyls. See Danen, W. C.; Neugebauer, F. A. Angew. Chem., Int. Ed. Engl. 1975, 14, 783-789.
23. Note that all structures with φ = 90° will have equal energy irrespective of their ψ angles.
24. See Table 2 in Ingold, K. U.; Wright, J. S. J. Chem. Educ. 2000, 77, 1062-1064.
25. Lunazzi, L.; Magagnoli, C.; Guerra, M.; Macciantelli, D. Tetrahedron Lett. 1979, 3031-3032.
26. (b) Lunazzi, L.; Magagnoli, C.; Macciantelli, D. J. Chem. Soc., Perkin Trans. 2 1980, 1704-1707.
27. ‡ = 2 ± 1.5 cal/mol/K. The inversion barrier for aniline is much lower (1.6 kcal/mol).
28. Brand, J. C. D.; Williams, D. R.; Cook, T. J. J. Mol. Spectrosc. 1966, 20, 359-380.
29. ̇ is delocalized into the phenyl groups of the extent of ca. 60%; see Neugebauer, F. A.; Bamberger, S. Angew. Chem., Int. Ed. Engl. 1971, 10, 71.
30. 3CN.
31. Porter, G.; Ward, B. J. Chim. Phys. 1964, 61, 1514-1522.
32. (b) Porter, G.; Strachan, E. Spectrochim. Acta 1958, 12, 299-304.
33. (c) Land, E. J.; Porter, G. Trans. Faraday Soc. 1963, 59, 2027-2037.
34. Radziszewski, J. G.; Gil, M.; Gorski, A.; Spanget-Larsen, J.; Waluk, J.; Mróz, B. J. J. Chem. Phys. 2001, 115, 9733-9738.
35. Dewar, M. J. S.; Zoebisch, E. G.; Healy, E. F.; Stewart, J. J. J. Am. Chem. Soc. 1985, 107, 3902-3909.
36. Neugebauer, F. A.; Bamberger, S. Chem. Ber. 1974, 107, 2362-2382.
37. 3 in an NMR tube.