Orbital phase control of the stabilities of π-conjugated diradicals

Bulletin of the Chemical Society of Japan

Volumn 69, Issue 10, 1996, Pages 2781-2789

  Iwase, Koji ^a   Inagaki, Satoshi ^a  

^a GIFU UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000245548     PISSN: 00092673     EISSN: None     Source Type: Journal    
DOI: 10.1246/bcsj.69.2781     Document Type: Article

References (54)

1. a) S. Inagaki and Y. Hirabayashi, Chem. Lett., 1982, 709;
2. b) S. Inagaki, H. Kawata, and Y. Hirabayashi, Bull. Chem. Soc. Jpn., 55, 3724 (1982);
3. c) S. Inagaki, H. Kawata, and Y. Hirabayashi, J. Org. Chem., 48, 2928 (1983);
4. d) S. Inagaki, K. Iwase, and H. Kawata, Bull. Chem. Soc. Jpn., 58, 601 (1985);
5. e) S. Inagaki, K. Iwase, and N. Goto, J. Org. Chem., 51, 362 (1986).
6. S. Inagaki, Bull. Chem. Soc. Jpn., 57, 3599 (1984).
7. S. Sakai and S. Inagaki, J. Am. Chem. Soc., 112, 7961 (1990).
8. K. Iwase, S. Sakai, and S. Inagaki, Chem. Lett., 1994, 1601.
9. a) L. Salem, "Electrons in Chemical Reactions: First Principles," Wiley, New York (1982);
10. b) J. Michl and V. Bonac̃ić-Koutecký, "Electronic Aspects of Organic Photochem istry," Wiley, New York (1990).
11. a) W. T. Borden, "Diradicals," Wiley, New York (1982);
12. b) H. Iwamura, Adv. Phys. Org. Chem., 26, 179 (1990).
13. a) W. T. Borden and E. R. Davidson, J. Am. Chem. Soc., 99, 4587 (1977).
14. b) E. R. Davidson, W. T. Borden, and J. Smith, J. Am. Chem. Soc., 100, 3299 (1978);
15. c) W. T. Borden, Mol. Cryst. Liq. Cryst., 232, 195 (1993).
16. A. A. Ovchinnikov, Theor. Chim. Acta, 47, 297 (1978). See also: J.-P. Malrieu, in "Theoretical Models of Chemical Bonding," ed by Z. B. Maksić, Springer, Berlin and Heiderberg (1990), Part 2, pp. 107-136.
17. A. A. Ovchinnikov, Theor. Chim. Acta, 47, 297 (1978). See also: J.-P. Malrieu, in "Theoretical Models of Chemical Bonding," ed by Z. B. Maksić, Springer, Berlin and Heiderberg (1990), Part 2, pp. 107-136.
18. T. P. Radhakrishnan, Chem. Phys. Lett., 181, 455 (1991).
19. Preliminary communication: K. Iwase, and S. Iagaki, Chem. Lett., 1993, 1619.
20. s=0, -1.
21. K. Fukui and S. Inagaki, J. Am. Chem. Soc., 97, 4445 (1975).
22. b) S. Inagaki, H. Fujimoto, and K. Fukui, J. Am. Chem. Soc., 98, 4693 (1976).
23. β or π-q-π* interaction.
24. α or π-q-π* interaction.
25. α- or -π-p-π*-q- interaction (Fig. 3a) occurs.
26. 11) while the sign is opposite. This gives the inequality 3.
27. D. Döhnert and J. Koutecký, J. Am. Chem. Soc., 102, 1789 (1980).
28. D. A. Dixon, T. H. Dunning, Jr., R. A. Eades, and D. A. Kleier, J. Am. Chem. Soc., 103, 2878 (1981).
29. M. Aoyagi, Y. Osamura, and S. Iwata, J. Chem. Phys., 83, 1140 (1985).
30. a) S. Inagaki, K. Iwase, and Y. Mori, Chem. Lett., 1986, 417;
31. b) S. Inagaki, Y. Mori, and N. Goto, Bull. Chem. Soc. Jpn., 63, 1098 (1990);
32. c) S. Inagaki, N. Goto, and K. Yoshikawa, J. Am. Chem. Soc., 113, 7144 (1991);
33. d) S. Inagaki, K. Yoshikawa, and Y. Hayano, J. Am. Chem. Soc., 115, 3706 (1993);
34. e) S. Inagaki, Y. Ishitani, and T. Kakefu, J. Am. Chem. Soc., 116, 5954 (1994).
35. ik and the CI expansion coefficient are summed up for all the CI configurations.
36. In the MCSCF (ij) calculations the active space has i active electrons in j active orbitals. The STO-3G basis set was employed in the calculations, which were carried out with the Gaussian 92 program; M. J. Frisch, G. W. Trucks, M. Head-Gordon, P. M. W. Gill, M. W. Wong, J. B. Foresman, B. G. Johnson, H. B. Schlegel, M. A. Robb, E. S. Replogle, R. Gomperts, J. L. Andres, K. Raghavachari, J. S. Binkley, C. Gonzalez, R. L. Martin, D. J. Fox, D. J. Defrees, J. Baker, J. J. P. Stewart, and J. A. Pople, Gaussian, Inc., Pittsburgh, PA (1992).
37. R. J. Baseman, D. W. Pratt, M. Chow, and P. Dowd, J. Am. Chem. Soc., 98, 5726 (1976).
38. J. A. Berson, in "Diradicals," ed by W. T. Borden, Wiley, New York (1982), pp. 151-194.
39. S. Kato, K. Morokuma, D. Feller, E. R. Davidson, and W. T. Borden, J. Am. Chem. Soc., 105, 1791 (1983).
40. B. B. Wright and M. S. Platz, J. Am. Chem. Soc., 105, 628 (1983).
41. Recently, its nitroxide analog was found to have a high-spin ground state: T. Ishida and H. Iwanura, J. Am. Chem. Soc., 113, 4238 (1991).
42. a) P. Nachigall and D. Jordan, J. Am. Chem. Soc., 115, 270 (1993);
43. b) P. Du and W. T. Borden, J. Am. Chem. Soc., 109, 930 (1987).
44. 28a)
45. a) P. Dowd, W. Chang, and Y. H. Paik, J. Am. Chem. Soc., 108, 7416 (1985);
46. b) W. R. Roth, U. Kowalczik, G. Maier, H. P. Reizenauer, R. Sustmann, and W. Muller, Angew. Chem., Int. Ed. Engl., 26, 1285 (1987).
47. P. M. Lahti, A. S. Ichimura, and J. A. Berson, J. Org. Chem., 54, 958 (1989);
48. b) P. M. Lahti, A. R. Rossi, and J. A. Berson, J. Am. Chem. Soc., 107, 2273 (1985).
49. P. Nachtigall, P. Dowd, and D. Jordan, J. Am. Chem. Soc., 114, 4747 (1992).
50. Y. Osamura, W. T. Borden, and K. Morokuma, J. Am. Chem. Soc., 106, 5112 (1984).
51. M. B. Coolidge, K. Yamashita, K. Morokuma, and W. T. Borden, J. Am. Chem. Soc., 112, 1751 (1990).
52. a) A. S. Ichimura, P. M. Lahti, and A. R. Matlin, J. Am. Chem. Soc., 112, 2868 (1990);
53. b) T. Hirano, T. Kumagai, T. Miyashi, K. Akiyama, and Y. Ikegami, J. Org. Chem., 56, 1907 (1991).
54. P. Du, D. A. Horvaot, and W. T. Borden, J. Am. Chem. Soc., 111, 3773 (1989).