Dications of Fluorenylidenes: Conformational and Electronic Effects on the Paratropicity/Antiaromaticity of Fluorenyl Cations with Cyclic Substituents

Journal of Organic Chemistry

Volumn 62, Issue 26, 1997, Pages 9318-9322

  Mills, Nancy S ^a   Malandra, James L ^a   Burns, Ellen E ^a   Green, Andrew ^a   Unruh, Karen E ^a   Kadlecek, Daniel E ^a   Lowery, John A ^a  

^a TRINITY UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 1542527737     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo971716o     Document Type: Article

References (33)

1. Breslow, R. Chem. Eng. News 1965, 43 (June 28), 90.
2. Breslow, R. Acc. Chem. Res 1973, 6, 393-398.
3. Malandra, J. L.; Mills, N. S.; Kadlecek, D. E.; Lowery, J. A. J. Am. Chem. Soc. 1994, 116, 11622-11624.
4. Amyes, T. L.; Richard, J. P.; Novak, M. J. Am. Chem. Soc. 1992, 114, 8032-8041.
5. Minsky, A.; Meyer, A. Y.; Rabinovitz, M. Tetrahedron 1985, 41, 785-791.
6. Müllen, K.; Meul, T.; Schade, P.; Schmickler, H.; Vogel, E. J. Am. Chem. Soc. 1987, 109, 4992-5003.
7. Eliasson, B.; Edlund, U. J. Chem. Soc., Perkin Trans. 2 1986, 937-940.
8. Eliasson, B.; Johnels, D.; Sethson, I.; Edlund, U. J. Chem. Soc., Perkin Trans 2 1990, 897-900.
9. Handoo, K. L.; Gadru, K. Ind. J. Chem. 1983, 22B, 909.
10. Agranat, I.; Rabinovitz, M.; Weissman, M. Tetrahedron Lett. 1972, 273-276.
11. Schonberg, A.; Sidky, M. M. J. Am. Chem. Soc. 1959, 81, 2259-2262.
12. Peterson, D. J. J. Org. Chem. 1968, 33, 780-784.
13. Falshaw, C. P.; Hashi, N. A.; Taylor, G. A. J. Chem. Soc., Perkin Trans. 1 1985, 1837-1843.
14. Safarzadeh-Amiri, A.; Verrall, R. E.; Steer, R. P. Can. J. Chem. 1983, 61, 894-899.
15. Mills, N. S.; Malandra, J. L.; Hensen, A.; Lowery, J. E. Polycyclic Arom. Comput. 1997, in press.
16. Rabinovitz, M.; Agranat, I.; Bergmann, E. D. Tetrahedron Lett. 1965, 1265-1296.
17. 1H NMR spectrum has peaks at 8.55 ppm (4H) and 9.07 ppm (1H). Olah, G. A.; Grant, J. L.; Spear, R. J.; Bollinger, J. M.; Serianz, A.; Sipos, G. J. Am. Chem. Soc. 1975, 98, 2501-2507.
18. Günther, H. NMR Spectroscopy, 2nd ed.; John Wiley and Sons, Inc.: New York, 1995.
19. Dewar, M. J. S.; Zoebisch, E. G.; Healy, E. F.; Stewart, J. J. P. J. Am. Chem. Soc. 1985, 107, 3902-3909.
20. Gilbert, K. Serena Software, Bloomington, IN, 1989.
21. Available in Supporting Information.
22. The slight variation in chemical shift is probably related to the resolution of the spectra and the difficulty of accurately assigning chemical shift to relatively broad signals. Normally the spectra of these dications, although less well-resolved than the spectra of the neutral precursors, are sufficiently well-resolved to determine splitting (see Supporting Information). However, the presence of trace amounts of paramagnetic material appears to broaden the spectra on occasion.
23. Sohár, P. Nuclear Magnetic Resonance Spectroscopy; CRC Press: Boca Raton, FL, 1983; Vol. II.
24. Breitmaier, E.; Voelter, W. Carbon-13 NMR Spectroscopy, 3rd ed.; VCH: New York, 1987.
25. Olah, G. A.; Prakash, G. K. S.; Liang, G.; Westerman, P. W.; Kunde, K.; Chandrasekhar, J.; Schleyer, P. v. R. J. Am. Chem. Soc. 1980, 102, 4485-4492.
26. Lammertsma, K.; Güner, O. F.; Thibodeaux, A. F.; Schleyer, P. v. R. J. Am. Chem. Soc. 1989, 111, 8995-9002.
27. Lammertsma, K. Chem. Intermed. 1988, 9, 141-169.
28. Lammertsma, K.; Schleyer, P. v. R. J. Phys. Chem. 1988, 92, 881-886.
29. Olah, G. A.; Bruce, M. R.; Welch, J. Inorg. Chem. 1977, 16, 2637.
30. Schönberg, A.; Awad, A.; Latil, K. J. Chem. Soc. 1951, 1368-1369.
31. Luisa, M.; Franco, M. B.; Herold, B. J. J. Chem. Soc., Perkin Trans. 2 1988, 443-449.
32. Dications made at -90°C were easier to transfer to an NMR tube, and there was little change in the resolution of the spectra between -78 and -90°C.
33. Hehre, W. J. Wavefunction, Inc., Irvine, CA, 1994.