The oxyallyl diradical: Observation of the singlet and triplet state by negative-ion photoelectron spectroscopy

Angewandte Chemie - International Edition

Volumn 49, Issue 4, 2010, Pages 670-671

  Bettinger, Holger F ^a  

^a UNIVERSITY OF TÜBINGEN   (Germany)

Author keywords

Allylic compounds; Photoelectron spectroscopy; Radicals; Small ring systems; Transition states

Indexed keywords

ALLYLIC COMPOUNDS; CHEMICAL EQUATIONS; CYCLOPROPANONE; DIRADICALS; RING CLOSURES; SINGLET STATE; SMALL RING SYSTEMS; TRANSITION STATE; TRIPLET STATE;

CHEMICAL REACTIONS; ELECTRONS; ENERGY ABSORPTION; NEGATIVE IONS; PHOTOELECTRICITY; PHOTOIONIZATION; PHOTONS;

PHOTOELECTRON SPECTROSCOPY;

EID: 74849129639     PISSN: 14337851     EISSN: 15213773     Source Type: Journal    
DOI: 10.1002/anie.200905482     Document Type: Article

References (21)

1. a) P. J. Chenier, J. Chem. Educ. 1978, 55, 286;
2. b) C. R. Engel, Y. Mérand, J. Côté, J. Org. Chem. 1982, 47, 4485.
3. a) D. B. Sclove, J. F. Pazos, R. L. Camp, F. D. Greene, J. Am. Chem. Soc. 1970, 92, 7488;
4. b) T. S. Sorensen, F. Sun, Can. J. Chem. 1997, 75, 1030;
5. c) B. A. Hess, U. Eckart, J. Fabian, J. Am. Chem. Soc. 1998, 120, 12310.
6. a) A. G. Schultz, Pure Appl. Chem. 1988, 60, 981;
7. b) A. R. Matlin, CRC Handbook of Organic Photochemistry and Photobiology, 2nd ed., CRC, Boca Raton, 2004, p. 81-91
8. -1, see: C. A. Schalley, S. Blanksby, J. N. Harvey, D. Schröder, W. Zummack, J. H. Bowie, H. Schwarz, Eur. J. Org. Chem. 1998, 987.
9. a) P. Dowd, J. Am. Chem. Soc. 1966, 88, 2587. For a very interesting account of Professor Dowd's contributions of to the chemistry of diradicals the reader is referred to:
10. b) C. J, Cramer, J. Chem. Soc. Perkin Trans. 2 1998, 1007.
11. M. Cibulka, Doctoral Thesis, Justus-Liebig-Universität Gießen (Gießen), 1999. In this thesis (unsuccessful)attempts to generate 1 and some if its derivatives under the conditions of matrix isolation using a large number of precursors and experimental conditions are reported.
12. a) Y. Osamura, W. T. Borden, K. Morokuma, J. Am. Chem. Soc. 1984, 106, 5112;
13. b) M. B. Coolidge, K. Yamashita, K. Morokuma, W. T. Borden, J. Am. Chem. Soc. 1990, 112, 1751.
14. T. Ichino, S. M. Villano, A. J. Gianola, D. J. Goebbert, L. Velarde, A. Sanov, S. J. Blanksby, X. Zhou, D. A. Hrovat, W. T. Borden, W. C. Lineberger, Angew. Chem. 2009, 121, 8861;
15. Angew. Chem. Int. Ed. 2009, 48, 8509.
16. Prof. W. T. Borden, personal communication.
17. a) N. J. Turro, W. B. Hammond, J. Am. Chem. Soc. 1966, 88, 3672;
18. b) S. E. Schaafsma, H. Steinberg, T. J. De Boer, Recl. Trav. Chim. Pays-Bas 1966, 85, 1170.
19. Based on extended Hückel calculations Hoffmann concluded that cyclopropanone would be unstable towards opening to give the oxyallyl diradical (see a) R. Hoffmann, J. Am. Chem. Soc. 1968, 90, 1475). The structure of cyclopropanone was confirmed with the microwave study that showed that the hydrogen atoms do not lie in the same plane as the carbon atoms
20. (see: b) J. M. Pochan, J. E. Baldwin, W. H. Flygare, J. Am. Chem. Soc. 1969, 91, 1896).
21. D. Schröder, C. Heinemann, H. Schwarz, J. N. Harvey, S. Dua, S. J. Blanksby, J. H. Bowie, Chem. Eur. J. 1998, 4, 2550.