Photochemical isomerization reactions of cyanopyrroles: A theoretical study

Journal of Physical Chemistry A

Volumn 110, Issue 46, 2006, Pages 12653-12661

  Su, Ming Der ^a  

^a NATIONAL CHIAYI UNIVERSITY   (Taiwan)

Author keywords

[No Author keywords available]

Indexed keywords

ISOMERIZATION; MATHEMATICAL MODELS; MOLECULAR STRUCTURE; PHOTOCHEMICAL REACTIONS; TOPOLOGY;

CONICAL INTERSECTIONS; ORBITAL TOPOLOGY MODELS; PHOTOTRANSPOSITIONS;

NITROGEN COMPOUNDS;

EID: 33846035818     PISSN: 10895639     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp063674q     Document Type: Article

References (26)

1. For reviews, see: (a) De. Mayo, P. In Rearrangements in Ground and Excited States; Academic Press: New York, 1980; Vol. 3, p 501.
2. (b) Buchardt, O. In Photochemistry of Heterocyclic Compounds; Wiley: New York, 1976.
3. (c) Kopecky, J. In Organic Photochemistry: A Visual Approach; VCH Publishers: New York, 1992.
4. Hiraoka, H. Chem. Commun. 1970, 1306.
5. Barltrop, J.; Day, A. C.; Moxon, P. D.; Ward, R. W. Chem. Commun. 1975, 786.
6. Barltrop, J.; Day, A. C.; Ward, R. W. Chem. Commun. 1978, 131.
7. Behrens, S.; Jug, K. J. Org. Chem. 1990, 55, 2288.
8. (a) Bernardi, F.; Olivucci, M.; Robb, M. A. Isr. J. Chem. 1993, 265.
9. (b) Kiessinger, M. Angew. Chem., Int. Ed. Engl. 1995, 34, 549.
10. (c) Bernardi, F.; Olivucci, M.; Robb, M. A. Chem. Soc. Rev. 1996, 321.
11. (d) Bernardi, F.; Olivucci, M.; Robb, M. A. J. Photochem. Photobio. A: Chem. 1997, 105, 365.
12. (e) Klessinger, M. Pure Appl. Chem. 1997, 69, 773.
13. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Montgomery, J. A., Jr.; Vreven, T.; Kudin, K. N.; Burant, J. C.; Millam, J. M.; Iyengar, S. S.; Tomasi, J.; Barone, V.; Mennucci, B.; Cossi, M.; Scalmani, G.; Rega, N.; Petersson, G. A.; Nakatsuji, H.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Klene, M.; Li, X.; Knox, J. E.; Hratchian, H. P.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Ayala, P. Y.; Morokuma, K.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Zakrzewski, V. G.; Dapprich, S.; Daniels, A. D.; Strain, M. C.; Farkas, O.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Ortiz, J. V.; Cui, Q.; Baboul, A. G.; Clifford, S.; Cioslowski, J.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; 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.; Gonzalez, C.; Pople, J. A. Gaussian 03, revision x.xx; Gaussian, Inc.: Pittsburgh, PA, 2003.
14. Bearpark, M. J.; Robb, M. A.; Schlegel, H. B. Chem. Phys. Lett. 1994, 225, 269.
15. McDouall, J. J. W.; Peasley, K.; Robb, M. A. Chem. Phys. Lett. 1988, 148, 183.
16. Jorgensen, W. J.; Salem L. In The Organic Chemist's Book of Orbitals; Academic Press: New York, 1973; pp 231.
17. Anderson, H. J. Can. J. Chem. 1959, 37, 2053.
18. 1 excited state created by direct excitation of a cyanopyrrole is a vertical state with the same geometry as the ground state (So) molecule, (b) An excited state with geometry identical to the ground state is called a Franck-Condon (FC) state.
19. The C-C, C-N, C-H, and N-H bonds in 2-cyanopyrrole (1) are fixed to be 1.35, 1.35, 1.09, and 1.09 Å, respectively. Also, the CCC, CNC, HCC, HNC, and CCN bond angles are fixed to be 108, 108, 126, 126, and 180°, respectively.
20. Xantheas, S. S.; Rudenberg, K. J. Chem. Phys. 1991, 95, 1862.
21. (a) Gerhartz, W.; Poshusta, R. D.; Michl, J. J. Am. Chem. Soc. 1977, 99, 4263.
22. (b) Olivucci, M.; Ragazos, I. N.; Bernardi, F.; Robb, M. A. J. Am. Chem. Soc. 1993, 115, 3710.
23. (c) Olivucci, M.; Bernardi, F.; Celani, P.; Ragazos, I. N.; Robb, M. A. J. Am. Chem. Soc. 1994, 116, 1077.
24. In contrast to a [1,3] sigmatropic hydrogen migration, the migration of the NH group is Woodward-Hoffmann allowed since a p orbital at nitrogen is participating in the reaction which allows a change of sign of the concerted molecular orbital.
25. Albright, T. A.; Burdett, J. K.; Whangbo, M. H. Orbital Interaction in Chemistry; Wiley: New York, 1985; pp 84.
26. Su, M.-D. J. Phys. Chem. A 2006, 110, 9420.