Carbazolyl nitrenium ion: Electron configuration and antiaromaticity assessed by laser flash photolysis, trapping rate constants, product analysis, and computational studies

Journal of Organic Chemistry

Volumn 72, Issue 22, 2007, Pages 8186-8195

  Winter, Arthur H ^a   Gibson, Harry H ^b   Falvey, Daniel E ^a  

^a Bldg 142   (United States)

^b AUSTIN COLLEGE   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CARBAZOLYL NITRENIUM ION; COMPUTATIONAL STUDIES; ELECTRON CONFIGURATION; LASER FLASH PHOTOLYSIS;

ABSORPTION SPECTRA; COMPUTATIONAL METHODS; LASER RADIATION; PHOTOLYSIS; SPECTROSCOPIC ANALYSIS;

IONS;

1 (CARBAZOL 9 YL) 2,4,6 TRIMETHYLPYRIDINIUM TETRAFLUOROBORATE; CARBAZOLYL NITRENIUM ION; ION; NITROGEN DERIVATIVE; PYRIDINIUM DERIVATIVE; UNCLASSIFIED DRUG;

AB INITIO CALCULATION; ARTICLE; CHEMICAL ANALYSIS; CHEMICAL REACTION; CHEMICAL REACTION KINETICS; DENSITY FUNCTIONAL THEORY; ELECTRON TRANSPORT; GEOMETRY; PHOTOLYSIS; PROTON NUCLEAR MAGNETIC RESONANCE;

EID: 35549006814     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo0708184     Document Type: Article

References (68)

1. Falvey, D. E. In Reactive Intermediates; Moss, R. A., Platz, M. S., Maitland Jones, J., Eds.; John Wiley & Sons: New York, 2004.
2. Falvey, D. E. J. Phys. Org. Chem. 1999, 12, 589-596.
3. Gassman, P. G. Acc. Chem. Res. 1970, 3, 26-33.
4. Abramovitch, R. A.; Davis, B. A. Chem. Rev. 1964, 64, 149-185.
5. Kennedy, S. A.; Novak, M.; Kolb, B. A. J. Am. Chem. Soc. 1997, 119, 7654-7664.
6. Thomas, S. I.; Falvey, D. E. J. Phys. Org. Chem. 2006, 19, 291-294.
7. Famulok, M.; Boche, G. Angew. Chem., Int. Ed. Engl. 1989, 28, 468-469.
8. Famulok, M.; Bosold, F.; Boche, G. Angew. Chem., Int. Ed. Engl. 1989, 28, 337-338.
9. Miller, J. A. Cancer Res. 1970, 30, 1570-1579.
10. Wei, Y.; Tang, X.; Sun, Y. J. Polym. Sci. Part A: Chem. 1989, 27, 2385-2396.
11. Wei, Y.; Jang, G.-W.; Chan, C.-C.; Hsueh, K. F.; Hariharan, R.; Patel, S. A.; Whitecar, C. K. J. Phys. Chem. 1990, 94, 7716-7721.
12. Waldrop, D. J.; Basak, A. Org. Lett. 2001, 3, 1053-1056.
13. Abramovitch, R. A.; Ye, X.; Pennington, W. T.; Schimek, G.; Bogdal, D. J. Org. Chem. 2000, 65, 343-351.
14. Abramovitch, R. A.; Ye, X. J. Org. Chem. 1999, 64, 5904-5912.
15. Waldrop, D. J.; Zhang, W. Org. Lett. 2001, 3, 2353-2356.
16. Saunders, M.; Berger, R.; Jaffe, A.; McBride, J. M.; O'Neill, J.; Breslow, R. J. M.; Hoffman, J. J. Am. Chem. Soc. 1973, 95, 3017-3018.
17. Amyes, T. L.; Richard, J. P.; Novak, M. J. Am. Chem. Soc. 1992, 114, 8032-8041.
18. Allen, A. D.; Tidwell, T. T. Chem. Rev. 2001, 101, 1333-1348.
19. Breslow, R.; Chang, H. W.; Hill, R.; Wasserman, E. J. Am. Chem. Soc. 1967, 89, 1112-1119.
20. Allen, A. D.; Fujio, M.; Mohammed, N.; Tidwell, T. T.; Tsuji, Y. J. Org. Chem. 1997, 62, 246-252.
21. Herndon, W. C.; Mills, N. S. J. Org. Chem. 2005, 70, 8492-8496.
22. Jiao, H.; Schleyer, P. v. R.; Mo, Y.; McAllister, M. A.; Tidwell, T. T. J. Am. Chem. Soc. 1997, 119, 7075-7083.
23. Sparrapan, R.; Eberlin, M. N.; Augusti, R. Rap. Comm. Mass. Spectrom. 2005, 19, 1775-1778.
24. Bogdal, D. Heterocycles 2000, 53, 2679-2688.
25. Bogdal, D. ARKIVOK 2001, 6, 109-115.
26. Vinolle, J.; Gornitzka, H.; Maron, L.; Schoeller, W. W.; Bourissou, D.; Bertrand, G. J. Am. Chem. Soc. 2007, 129, 978-985.
27. Abramovitch, R. A.; Evertz, K.; Huttner, G.; Gibson, H. H.; Weems, H. G. J. Chem. Soc. Chem. Comm. 1988, 325-327.
28. Winter, A. H.; Thomas, S. I.; Kung, A. C.; Falvey, D. E. Org. Lett. 2004, 6, 4671-4674.
29. McIlroy, S.; Falvey, D. E. J. Am. Chem. Soc. 2001, 123, 11329-11330.
30. 3CN and the more defined 570 nm peak of the radical relative to the 570 nm peak of the nitrenium ion. See Supporting Information for radical spectrum and LFP of 4a in the presence of DMB. For a previously published spectrum, see: Dilabio, G. A.; Litwinienki, G.; Lin, S.; Pratt, D. A.; Ingold, K. U. J. Phys. Chem. A 2002, 106, 11719-11725.
31. For a paper on the reactions of the carbazolyl radical, see: Waters, W. A.; White, J. E. J. Chem. Soc. C: Organic 1968, 6, 740-745.
32. Shida, T. Electronic Absorption Spectra of Radical Ions; Elsevier: Amsterdam, 1988.
33. 3CN (SCE reference). See Nie, G.; Xu, J.; Zhang, S.; Han, X. J. Appl. Electrochem. 2006, 36, 937-944.
34. Based on photolysis performed using 350 nm bulbs; 254 nm photolysis gave a complex mixture of products including 5 carbazole-collidine isomers, carbazole, collidine, and 2 TMB adducts. Many of these products from 254 nm photolysis presumably arise from secondary photolysis, chemistry resulting from excitation of TMB, or reactions with accumulated photoproducts.
35. diff by a factor of ∼2 due to assumptions about the radii of the reacting species.
36. Hawari, J. A.; Engel, P. S.; Griller, D. Chem. Kinet. 1985, 17, 1215-1219.
37. Thomas, S. I.; Falvey, D. E. J. Org. Chem. 2006, 72, 4626-4634.
38. 3CN and for the halogenated diarylnitrenium ions at 400-420 nm. See Thomas, S. I.; Falvey, D. E. J. Org. Chem. 2006, 72, 4626-4634,
39. and McIlroy, S.; Falvey, D. E. J. Am. Chem. Soc. 2001, 123, 11329-11330.
40. Winter, A. H.; Falvey, D. E.; Cramer, C. J. J. Am. Chem. Soc. 2004, 126, 9661-9668.
41. Cramer, C. J. Essentials of Computational Chemistry: Theories and Models, 2nd ed.; John Wiley & Sons: Chichester, 2004.
42. Cramer, C. J.; Truhlar, D. G.; Falvey, D. E. J. Am. Chem. Soc. 1997, 119, 12338-12342.
43. McIlroy, S.; Cramer, C. J.; Falvey, D. E. Org. Lett. 2000, 2, 2451-2454.
44. Kung, A. C.; McIlroy, S.; Falvey, D. E. J. Org. Chem. 2005, 70, 5283-5290.
45. Borden, W. T.; Gritsan, N. P.; Hadad, C. M.; Karney, W. L.; Kemnitz, C. R.; Platz, M. S. Acc. Chem. Res. 2000, 33, 765-771.
46. Gritsan, N. P.; Platz, M. S. Chem. Rev. 2006, 106, 3844-3867.
47. Scheschkewitz, D.; Amii, H.; Gornitzka, H.; Schoeller, W. W.; Bourissou, D.; Bertrand, G. Science 2002, 295, 1880-1881.
48. Perrin, C. L.; Rodgers, B. L.; O'Connor, J. M. J. Am. Chem. Soc. 2007, 129, 4795-4799.
49. Little, R. D.; Brown, L. M.; Masjedizadeh, M. R. J. Am. Chem. Soc. 1992, 114, 3071-3075.
50. Schleyer, P. Chem. Rev. 2001, 101, 1115-1117.
51. Gomes, J. A. N. F.; Mallion, R. B. Chem. Rev. 2001, 101, 1349-1383.
52. Mitchell, R. H. Chem. Rev. 2001, 101, 1301-1315.
53. Krygowski, T. M.; Cyranski, M. K. Chem. Rev. 2001, 101, 1385-1419.
54. Chen, Z.; Wannere, C. S.; Corminboeuf, C.; Puchta, R.; Schleyer, P. v. R. Chem. Rev. 2005, 105, 3842-3888.
55. Dauben, H. J.; Wilson, J. D.; Laity, J. L. J. Am. Chem. Soc. 1968, 90, 811-813.
56. Krygowski, T. M.; Cyranski, M. K. Tetrahedron 1999, 55, 11143-11148.
57. Katritzky, A.; Jug, K.; Oniciu, D. C. Chem. Rev. 2001, 101, 1421-1449.
58. Cioslowski, J. J. Am. Chem. Soc. 1989, 111, 8333-8336.
59. Stanger, A. J. Org. Chem. 2006, 71, 883-893.
60. Mills, N. S.; Llagostera, K. B.; Tirla, C.; Gordon, S. M.; Carpenetti, D. J. Org. Chem. 2006, 71, 7939-7946.
61. Schleyer, P. v. R.; Puhlhofer, F. Org. Lett. 2002, 4, 2873-2876.
62. Bally, T. Angew. Chem., Int. Ed. 2006, 45, 6616-6619.
63. Frisch, M. J. T.; et al. Gaussian03, revision B.03; Gaussian, Inc.: Pittsburgh, PA, 2003.
64. Becke, A. D. Phys. Rev. A 1988, 38, 3098-3100.
65. Becke, A. D. J. Chem. Phys. 1993, 98, 5648-5652.
66. Stevens, P. J.; Devlin, F. J.; Chabalowski, C. F.; Frisch, M. J. J. Phys. Chem. 1994, 98, 11632-11627.
67. Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B 1988, 37, 785-789.
68. Bonesi, S. M.; Erra-Balsells, R. J. Het. Chem. 1997, 34, 877-889.