Endohedral Homoconjugation in Cyclopentadiene Embedded in C60. Theoretical and Electrochemical Evidence

Journal of Organic Chemistry

Volumn 62, Issue 23, 1997, Pages 7912-7913

  Iikura, Hitoshi ^a   Mori, Seiji ^a   Sawamura, Masaya ^a   Nakamura, Eiichi ^a  

^a UNIVERSITY OF TOKYO   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000752260     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo971025s     Document Type: Article

References (19)

1. Sawamura, M.; Iikura, H.; Nakamura, E. J. Am. Chem. Soc. 1996, 118, 12850.
2. Avent, A. G.; Birkett, P. R.; Crane, J. D.; Darwish, A. D.; Langley, G. J.; Kroto, H. W.; Taylor, R.; Walton, D. R. M. J. Chem. Soc., Chem. Commun. 1994, 1463.
3. 3 carbon atoms).
4. (a) 3-21G: Binkley, J. S.; Pople, J. A.; Hehre, W. J. J. Am. Chem. Soc. 1980, 102, 939. Dobbs, K. D.; Hehre, W. J. J. Comput. Chem. 1986, 7, 359.
5. (a) 3-21G: Binkley, J. S.; Pople, J. A.; Hehre, W. J. J. Am. Chem. Soc. 1980, 102, 939. Dobbs, K. D.; Hehre, W. J. J. Comput. Chem. 1986, 7, 359.
6. (b) 3-21G(*): Pietro, W. J.; Francl, M. M.; Hehre, W. J.; DeFrees, D. J.; Pople, J. A.; Binkley, J. S. J. Am. Chem. Soc. 1982, 104, 5039.
7. 5M (M = SiCp, etc.), see: Chistyakov, A. L.; Stankevich, I. V. Russ. Chem. Bull. 1996, 45, 2294.
8. Martin, H.-D.; Mayer, B. Angew. Chem., Int. Ed. Engl. 1983, 22, 283.
9. Reed, A. K.; Curtiss, L. A.; Weinhold, F. Chem. Rev. 1988, 88, 899.
10. + contained in the supporting electrolyte.
11. 60 may provide reference points: Lerke, S. A.; Parkinson, B. A.; Evans, D. H.; Fagan, P. J. J. Am. Chem. Soc. 1992, 114, 7807.
12. (b) For CV measurements of organofullerenes, see: Eiermann, M.; Wudl, F.; Prato, M.; Maggini, M. J. Am. Chem. Soc. 1994, 116, 8364. Cardullo, F.; Isaacs, L.; Diederich, F.; Gisselbrecht, J.-P.; Boudon, C.; Gross, M. J. Chem. Soc., Chem. Commun. 1996, 797. Murata, Y.; Motoyama, K.; Komatsu, K.; Wan, T. S. M. Tetrahedron 1996, 52, 5077.
13. (b) For CV measurements of organofullerenes, see: Eiermann, M.; Wudl, F.; Prato, M.; Maggini, M. J. Am. Chem. Soc. 1994, 116, 8364. Cardullo, F.; Isaacs, L.; Diederich, F.; Gisselbrecht, J.-P.; Boudon, C.; Gross, M. J. Chem. Soc., Chem. Commun. 1996, 797. Murata, Y.; Motoyama, K.; Komatsu, K.; Wan, T. S. M. Tetrahedron 1996, 52, 5077.
14. (b) For CV measurements of organofullerenes, see: Eiermann, M.; Wudl, F.; Prato, M.; Maggini, M. J. Am. Chem. Soc. 1994, 116, 8364. Cardullo, F.; Isaacs, L.; Diederich, F.; Gisselbrecht, J.-P.; Boudon, C.; Gross, M. J. Chem. Soc., Chem. Commun. 1996, 797. Murata, Y.; Motoyama, K.; Komatsu, K.; Wan, T. S. M. Tetrahedron 1996, 52, 5077.
15. Although we show the limiting structures such as 2 and 3 for the ease of understanding, they are an incorrect representation of the reality, where the two systems actually form a single π-electronic system. The seeming presence of Coulombic interactions between the upper and the lower halves must therefore be interpreted in terms of a delocalized electron system rather than the localized pictures of 2 and 3.
16. After the second cycle until the seventh scan, the voltammogram remains identical showing the presence of a small amount of 1, since a steady state was reached for the material exchange between the vicinity of the electrode and the bulk solution where excess 1 is present.
17. The same conclusion was reached when a narrower scan range (-0.70 to -1.95 V) or different scan rates (10 and 1000 mV/s) were employed.
18. 60 and its derivatives have not be reported to be very basic (ref 9).
19. 60-based metal ligand system, see: Yamago, S.; Yanagawa, M.; Mukai, H.; Nakamura, E. Tetrahedron 1996, 52, 5091.