Fulvalenes, Fulvenes, and Related Molecules: An ab Initio Study

Journal of Organic Chemistry

Volumn 62, Issue 7, 1997, Pages 2026-2038

  Scott, Anthony P ^a   Agranat, Israel ^b   Biedermann, P Ulrich ^b   Riggs, Noel V ^a   Radom, Leo ^a  

^a AUSTRALIAN NATIONAL UNIVERSITY   (Australia)

^b HEBREW UNIVERSITY OF JERUSALEM   (Israel)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0001446398     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo962407l     Document Type: Article

References (97)

1. For a recent comprehensive review on fulvenes and fulvalenes see: Neuenschwander, M. In The Chemistry of Functional Groups. Supplement A, The Chemistry of Double-Bonded Functional Groups; Patai, S., Ed.; Wiley: Chichester, 1989; Vol. 2, pp 1131-1268.
2. Reviews: (a) Becker, G. Triafulvenes. Methoden der Organischen Chemie Hauben Weyl, Georg Thieme Verlag: Stuttgart. Carbocyclische Pi-Elektronen Systeme, 1985; 5/2c, p 476. (b) Zeller, K. P. Pentafulvenes. Ibid. 1985, 5/2c, 504. (c) Asao, T.; Oda, M. Heptafulvenes. Ibid. 1985, 5/2c, 769. (d) Bergmann, E. D. Chem. Rev. 1968, 68, 41.
3. Reviews: (a) Becker, G. Triafulvenes. Methoden der Organischen Chemie Hauben Weyl, Georg Thieme Verlag: Stuttgart. Carbocyclische Pi-Elektronen Systeme, 1985; 5/2c, p 476. (b) Zeller, K. P. Pentafulvenes. Ibid. 1985, 5/2c, 504. (c) Asao, T.; Oda, M. Heptafulvenes. Ibid. 1985, 5/2c, 769. (d) Bergmann, E. D. Chem. Rev. 1968, 68, 41.
4. Reviews: (a) Becker, G. Triafulvenes. Methoden der Organischen Chemie Hauben Weyl, Georg Thieme Verlag: Stuttgart. Carbocyclische Pi-Elektronen Systeme, 1985; 5/2c, p 476. (b) Zeller, K. P. Pentafulvenes. Ibid. 1985, 5/2c, 504. (c) Asao, T.; Oda, M. Heptafulvenes. Ibid. 1985, 5/2c, 769. (d) Bergmann, E. D. Chem. Rev. 1968, 68, 41.
5. Reviews: (a) Becker, G. Triafulvenes. Methoden der Organischen Chemie Hauben Weyl, Georg Thieme Verlag: Stuttgart. Carbocyclische Pi-Elektronen Systeme, 1985; 5/2c, p 476. (b) Zeller, K. P. Pentafulvenes. Ibid. 1985, 5/2c, 504. (c) Asao, T.; Oda, M. Heptafulvenes. Ibid. 1985, 5/2c, 769. (d) Bergmann, E. D. Chem. Rev. 1968, 68, 41.
6. Synthesis: (a) Triafulvene: Billups, W. E.; Lin, L.-J.; Casserly, E. W. J. Am. Chem. Soc. 1984, 106, 3698. Staley, S. W.; Norden, T. D. J. Am. Chem. Soc. 1984, 106, 3699. Maier, G.; Hoppe, M.; Lanz, K.; Reisenauer, P. Tetrahedron Lett. 1984, 25, 5645. (b) Pentafulvene: Kent, J. E.; Jones, A. J. Aust. J. Chem. 1970, 23, 1059. (c) Heptafulvene: Schenk, W. K.; Kyburz, R.; Neuenschwander, M. Helv. Chim. Acta 1975, 58, 1099.
7. Synthesis: (a) Triafulvene: Billups, W. E.; Lin, L.-J.; Casserly, E. W. J. Am. Chem. Soc. 1984, 106, 3698. Staley, S. W.; Norden, T. D. J. Am. Chem. Soc. 1984, 106, 3699. Maier, G.; Hoppe, M.; Lanz, K.; Reisenauer, P. Tetrahedron Lett. 1984, 25, 5645. (b) Pentafulvene: Kent, J. E.; Jones, A. J. Aust. J. Chem. 1970, 23, 1059. (c) Heptafulvene: Schenk, W. K.; Kyburz, R.; Neuenschwander, M. Helv. Chim. Acta 1975, 58, 1099.
8. Synthesis: (a) Triafulvene: Billups, W. E.; Lin, L.-J.; Casserly, E. W. J. Am. Chem. Soc. 1984, 106, 3698. Staley, S. W.; Norden, T. D. J. Am. Chem. Soc. 1984, 106, 3699. Maier, G.; Hoppe, M.; Lanz, K.; Reisenauer, P. Tetrahedron Lett. 1984, 25, 5645. (b) Pentafulvene: Kent, J. E.; Jones, A. J. Aust. J. Chem. 1970, 23, 1059. (c) Heptafulvene: Schenk, W. K.; Kyburz, R.; Neuenschwander, M. Helv. Chim. Acta 1975, 58, 1099.
9. Synthesis: (a) Triafulvene: Billups, W. E.; Lin, L.-J.; Casserly, E. W. J. Am. Chem. Soc. 1984, 106, 3698. Staley, S. W.; Norden, T. D. J. Am. Chem. Soc. 1984, 106, 3699. Maier, G.; Hoppe, M.; Lanz, K.; Reisenauer, P. Tetrahedron Lett. 1984, 25, 5645. (b) Pentafulvene: Kent, J. E.; Jones, A. J. Aust. J. Chem. 1970, 23, 1059. (c) Heptafulvene: Schenk, W. K.; Kyburz, R.; Neuenschwander, M. Helv. Chim. Acta 1975, 58, 1099.
10. Synthesis: (a) Triafulvene: Billups, W. E.; Lin, L.-J.; Casserly, E. W. J. Am. Chem. Soc. 1984, 106, 3698. Staley, S. W.; Norden, T. D. J. Am. Chem. Soc. 1984, 106, 3699. Maier, G.; Hoppe, M.; Lanz, K.; Reisenauer, P. Tetrahedron Lett. 1984, 25, 5645. (b) Pentafulvene: Kent, J. E.; Jones, A. J. Aust. J. Chem. 1970, 23, 1059. (c) Heptafulvene: Schenk, W. K.; Kyburz, R.; Neuenschwander, M. Helv. Chim. Acta 1975, 58, 1099.
11. (a) Triafulvene: Norden, T. D.; Staley, S. W.; Taylor, W. H.; Harmony, M. D. J. Am. Chem. Soc. 1986, 108, 7912. See also: Hess, B. A., Jr.; Michalska, D.; Schaad, L. J. J. Am. Chem. Soc. 1985, 107, 1449.
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17. Reviews: (a) Becker, G. Triapentafulvalene. Methoden der Organischen Chemie Hauben Weyl; Carbocyclische Pi-Elektronen Systeme; Georg Thieme Verlag: Stuttgart, 1985; 5/2c, p 479. (b) Becker, G. Triaheptafulvalene. Ibid. 1985, 5/2c, p 485. (c) Becker, G. Pentafulvalene. Ibid. 1985, 5/2c, p 685. (d) Escher, A.; Rutsch, W.; Neuenschwander, M. Helv. Chim. Acta 1986, 69, 1644.
18. Reviews: (a) Becker, G. Triapentafulvalene. Methoden der Organischen Chemie Hauben Weyl; Carbocyclische Pi-Elektronen Systeme; Georg Thieme Verlag: Stuttgart, 1985; 5/2c, p 479. (b) Becker, G. Triaheptafulvalene. Ibid. 1985, 5/2c, p 485. (c) Becker, G. Pentafulvalene. Ibid. 1985, 5/2c, p 685. (d) Escher, A.; Rutsch, W.; Neuenschwander, M. Helv. Chim. Acta 1986, 69, 1644.
19. Reviews: (a) Becker, G. Triapentafulvalene. Methoden der Organischen Chemie Hauben Weyl; Carbocyclische Pi-Elektronen Systeme; Georg Thieme Verlag: Stuttgart, 1985; 5/2c, p 479. (b) Becker, G. Triaheptafulvalene. Ibid. 1985, 5/2c, p 485. (c) Becker, G. Pentafulvalene. Ibid. 1985, 5/2c, p 685. (d) Escher, A.; Rutsch, W.; Neuenschwander, M. Helv. Chim. Acta 1986, 69, 1644.
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26. Reviews: (a) Pietra, P. Chem. Rev. 1973, 73, 294. (b) Becker, G. Pentaheptafulvalene. Methoden der Organischen Chemie Hauben Weyl, Carbocyclische Pi-Elektronen Systeme; Georg Thieme Verlag: Stuttgart, 1985; 5/2c, p 781. Becker, G. Heptafulvalene. Ibid. 1985; B/2c, p 697.
27. Reviews: (a) Pietra, P. Chem. Rev. 1973, 73, 294. (b) Becker, G. Pentaheptafulvalene. Methoden der Organischen Chemie Hauben Weyl, Carbocyclische Pi-Elektronen Systeme; Georg Thieme Verlag: Stuttgart, 1985; 5/2c, p 781. Becker, G. Heptafulvalene. Ibid. 1985; B/2c, p 697.
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63. Experimental (see reference 26): A = 8426, B = 8226, C = 4271 MHz. HF: A = 8572, B = 8268, C = 4319 MHz. B-LYP: A = 8316, B = 8104, C = 4212 MHz. MP2: A = 8435, B = 8251, C = 4281 MHz.
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93. 2 symmetry) are given in the Supporting Information.
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97. For a discussion on the significance of the dipole moments of the triapentafulvalenes from the point of view of the "aromaticity", see: Agranat, I. In MTP Int. Rev. Sci., Organic Chemistry, Series One, Vol. 3, Aromatic Compounds; Zollinger, H., Ed.; Butterworths: London, 1973; p 139.