An ESR study of a tetrasilaspirobiindane anion radical. Stereoelectronic electron-accepting effects of trialkylsilyl groups

Chemistry Letters

Volumn , Issue 4, 1999, Pages 317-318

  Setaka, Wataru ^a   Kabuto, Chizuko ^a   Kira, Mitsuo ^a  

^a TOHOKU UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0033474538     PISSN: 03667022     EISSN: None     Source Type: Journal    
DOI: 10.1246/cl.1999.317     Document Type: Article

References (20)

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8. For a recent discussion on electron-accepting effects of silyl substituents, see: Y. Apeloig, in "The Chemistry of Organic Silicon Compounds," ed by S. Patai and Z. Rappoport, John Wiley, New York (1989), Part 1, Chap. 2.
9. 4: C, 63.56; H, 8.13%.
10. o).
11. A number of radical anions of spiro compounds having two perpendicular π systems have been investigated by ESR spectroscopy. Whether the spin delocalization occurs over the two π systems or not is dependent on the molecular structure and the generation conditions: R. D. Cowell and G. Urry, J. Chem. Phys., 38, 2028 (1963); F. Gerson, R. Gleiter, G. Moshuk, and A. S. Dreiding, J. Am. Chem. Soc., 94, 2919 (1972); F. Gerson, B. Kowert, and B. M. Peake, J. Am. Chem. Soc., 96, 118 (1974); H. Sakurai, T. Koyama, M. Kira, A. Hosomi, and Y. Nakadaira, Tetrahedron Lett., 23, 543 (1982); P. Maslak, M. P. Augustine, and J. D. Burkey, J. Am. Chem. Soc., 112, 5359 (1990); K. Ueda, M. Yamanoha, T. Sugimoto, H. Fujita, A. Ugawa, K. Yakushi, and K. Kano, Chem. Lett., 1997, 461.
12. A number of radical anions of spiro compounds having two perpendicular π systems have been investigated by ESR spectroscopy. Whether the spin delocalization occurs over the two π systems or not is dependent on the molecular structure and the generation conditions: R. D. Cowell and G. Urry, J. Chem. Phys., 38, 2028 (1963); F. Gerson, R. Gleiter, G. Moshuk, and A. S. Dreiding, J. Am. Chem. Soc., 94, 2919 (1972); F. Gerson, B. Kowert, and B. M. Peake, J. Am. Chem. Soc., 96, 118 (1974); H. Sakurai, T. Koyama, M. Kira, A. Hosomi, and Y. Nakadaira, Tetrahedron Lett., 23, 543 (1982); P. Maslak, M. P. Augustine, and J. D. Burkey, J. Am. Chem. Soc., 112, 5359 (1990); K. Ueda, M. Yamanoha, T. Sugimoto, H. Fujita, A. Ugawa, K. Yakushi, and K. Kano, Chem. Lett., 1997, 461.
13. A number of radical anions of spiro compounds having two perpendicular π systems have been investigated by ESR spectroscopy. Whether the spin delocalization occurs over the two π systems or not is dependent on the molecular structure and the generation conditions: R. D. Cowell and G. Urry, J. Chem. Phys., 38, 2028 (1963); F. Gerson, R. Gleiter, G. Moshuk, and A. S. Dreiding, J. Am. Chem. Soc., 94, 2919 (1972); F. Gerson, B. Kowert, and B. M. Peake, J. Am. Chem. Soc., 96, 118 (1974); H. Sakurai, T. Koyama, M. Kira, A. Hosomi, and Y. Nakadaira, Tetrahedron Lett., 23, 543 (1982); P. Maslak, M. P. Augustine, and J. D. Burkey, J. Am. Chem. Soc., 112, 5359 (1990); K. Ueda, M. Yamanoha, T. Sugimoto, H. Fujita, A. Ugawa, K. Yakushi, and K. Kano, Chem. Lett., 1997, 461.
14. A number of radical anions of spiro compounds having two perpendicular π systems have been investigated by ESR spectroscopy. Whether the spin delocalization occurs over the two π systems or not is dependent on the molecular structure and the generation conditions: R. D. Cowell and G. Urry, J. Chem. Phys., 38, 2028 (1963); F. Gerson, R. Gleiter, G. Moshuk, and A. S. Dreiding, J. Am. Chem. Soc., 94, 2919 (1972); F. Gerson, B. Kowert, and B. M. Peake, J. Am. Chem. Soc., 96, 118 (1974); H. Sakurai, T. Koyama, M. Kira, A. Hosomi, and Y. Nakadaira, Tetrahedron Lett., 23, 543 (1982); P. Maslak, M. P. Augustine, and J. D. Burkey, J. Am. Chem. Soc., 112, 5359 (1990); K. Ueda, M. Yamanoha, T. Sugimoto, H. Fujita, A. Ugawa, K. Yakushi, and K. Kano, Chem. Lett., 1997, 461.
15. A number of radical anions of spiro compounds having two perpendicular π systems have been investigated by ESR spectroscopy. Whether the spin delocalization occurs over the two π systems or not is dependent on the molecular structure and the generation conditions: R. D. Cowell and G. Urry, J. Chem. Phys., 38, 2028 (1963); F. Gerson, R. Gleiter, G. Moshuk, and A. S. Dreiding, J. Am. Chem. Soc., 94, 2919 (1972); F. Gerson, B. Kowert, and B. M. Peake, J. Am. Chem. Soc., 96, 118 (1974); H. Sakurai, T. Koyama, M. Kira, A. Hosomi, and Y. Nakadaira, Tetrahedron Lett., 23, 543 (1982); P. Maslak, M. P. Augustine, and J. D. Burkey, J. Am. Chem. Soc., 112, 5359 (1990); K. Ueda, M. Yamanoha, T. Sugimoto, H. Fujita, A. Ugawa, K. Yakushi, and K. Kano, Chem. Lett., 1997, 461.
16. A number of radical anions of spiro compounds having two perpendicular π systems have been investigated by ESR spectroscopy. Whether the spin delocalization occurs over the two π systems or not is dependent on the molecular structure and the generation conditions: R. D. Cowell and G. Urry, J. Chem. Phys., 38, 2028 (1963); F. Gerson, R. Gleiter, G. Moshuk, and A. S. Dreiding, J. Am. Chem. Soc., 94, 2919 (1972); F. Gerson, B. Kowert, and B. M. Peake, J. Am. Chem. Soc., 96, 118 (1974); H. Sakurai, T. Koyama, M. Kira, A. Hosomi, and Y. Nakadaira, Tetrahedron Lett., 23, 543 (1982); P. Maslak, M. P. Augustine, and J. D. Burkey, J. Am. Chem. Soc., 112, 5359 (1990); K. Ueda, M. Yamanoha, T. Sugimoto, H. Fujita, A. Ugawa, K. Yakushi, and K. Kano, Chem. Lett., 1997, 461.
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18. 6; these values are good in accord with the experimental spin densities.
19. ESREXN program is used for simulation. Heinzer, J; QCPE No.209 (1972).
20. -1, in 2-MeTHF and DME, respectively. The higher AH‡ value in 2-MeTHF may be explained by the larger ion-pair interaction between the π anion radical and alkali metal ion.