Substituent effects on the structure and aromaticity of 4-silatriafulvene

Journal of Physical Chemistry A

Volumn 102, Issue 51, 1998, Pages 10530-10535

  Veszprémi, Tamás ^a,c   Takahashi, Masae ^a   Hajgató, Balazs ^c   Ogasawara, Jun ^b   Sakamoto, Kenkichi ^b   Kira, Mitsuo ^a,b  

^a INST OF PHYS AND CHEMICAL RESEARCH   (Japan)

^b TOHOKU UNIVERSITY   (Japan)

^c BUDAPEST UNIVERSITY OF TECHNOLOGY AND ECONOMICS   (Hungary)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0001542741     PISSN: 10895639     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp981761f     Document Type: Article

References (57)

1. (a) Staley, S. W.; Norden, T. D. J. Am. Chem. Soc. 1984, 106, 3699.
2. (b) Billups, W. E.; Lin, L.-J.; Casserly, E. W. J. Am. Chem. Soc. 1984, 106, 3698.
3. (c) Maier, G.; Hoppe, M.; Lanz, K.; Reisenauer, H. P. Tetrahedron Lett. 1984, 25, 5645.
4. Minkin, V. I.; Glukhovtsev, M. N.; Simkin, B. Ya. Aromaticity and Antiaromaticity: Electronic and Structural Aspects; Wiley: New York, 1994.
5. Norden, T. D.; Staley, S. W.; Taylor, W. H.; Harmony, M. D. J. Am. Chem. Soc. 1986, 108, 7912.
6. Schriver, G. W.; Fink, M. J., Gordon, M. S. Organometallics 1987, 6, 1977.
7. Staley, S. W.; Norden, T. D.; Taylor, W. H.; Harmony, M. D. J. Am. Chem. Soc. 1987, 109, 7641.
8. Bachrach, S. M. J. Org. Chem. 1990, 55, 4961.
9. Bachrach, S. M.; Liu, M. J. Phys. Org. Chem. 1991, 4, 242.
10. Burk, P., Abboud, J.-L. M.; Koppel, I. A. J. Phys. Chem. 1996, 100, 6992.
11. Fuchs, E.; Breit, B.; Heydt, H.; Schoeller, W.; Busch, T.; Krüger, C.; Betz, P.; Regitz, M. Chem. Ber. 1991, 124, 2843.
12. Scott, A. P.; Agranat, I.; Biedermann, P. U.; Riggs, N. V.; Radom, L. J. Org. Chem. 1997, 62, 2026.
13. (a) Breslow, R.; Haynie, R.; Mirra, J. J. Am. Chem. Soc. 1959, 81, 247.
14. (b) Breslow, R.; Eicher, T.; Krebs, A.; Peterson, R. A.; Posner, J. J. Am. Chem. Soc. 1965, 87, 1320.
15. (c) Breslow, R.; Altman, L. J.; Krebs, A.; Mohacsi, E.; Murata, I.; Peterson, R. A.; Posner, J. J. Am. Chem. Soc. 1965, 87, 1326.
16. (d) Krebs, A. W. Angew. Chem. Int. Ed. Engl. 1965, 4, 10.
17. Greenberg, A., Tomkins, R. P. T.; Dobrovolny, M.; Liebman, J. F. J. Am. Chem. Soc. 1983, 105, 6855.
18. Budzelaar, P. H. M.; Kraka, E.; Cremer, D.; Schleyer, P. v. R. J. Am. Chem. Soc. 1986, 108, 561.
19. (a) Clark, D. T.; Lilley, D. M. J. J. Chem. Soc., Chem. Commun. 1970, 147.
20. (b) Hase, H.-L., Müller, C.; Schweig, A. Tetrahedron 1978, 34, 2983.
21. (c) Fitzpatrick, N. J.; Fanning, M. O. J. Mol. Struct. 1975, 25, 197.
22. (d) Skancke, A. J. Mol. Struct. 1976, 30, 95.
23. (a) Hehre, W. J.; Pople, J. A. J. Am. Chem. Sac. 1975, 97, 6941.
24. (b) Herndon, W. C. Pure Appl. Chem. 1980, 52, 1459.
25. Fratev, F.; Bonchev, D.; Enchev, V. Croat. Chem. Acta 1980, 53, 545.
26. Sakamoto, K.; Ogasawara, J.; Sakurai, H.; Kira, M. J. Am. Chem. Soc. 1997, 119, 3405.
27. Bravo-Zhivotovskii, D.; Braude, V.; Stanger, A.; Kapon, M.; Apeloig, Y. Organometallics 1992, 11, 2326.
28. Veszprémi, T.; Takahashi, M.; Ogasawara, J.; Sakamoto, K.; Kira, M. J. Am. Chem. Soc. 1998, 120, 2408
29. Frish, M. J.; Truck, G. W.; Head-Gordon, M.; Gill, P. M. W.; Wong, W.; Foresman, J. B.; Johnson, B. G.; Schlegel, H. B.; Robb, M. A.; Repolgle, E. S.; Gompers, M.; Andrews, J. A.; Ragchavachari, K.; Binkley, J. S.; Gonzalez, C.; Martin, R. L.; Fox, D. J.; Defrees, J.; Baker, J.; Stewart, J. P.; Pople, J. A. GAUSSIAN 94; Gaussian Inc.: Pittsburgh, PA, 1994.
30. y are the single- and double-bond lengths between atoms X and Y, respectively. The index ΣCC is the sum of the C=C double bond characters in %. For a heterol derivatives, only three C-C bond distances are taken into account for the evaluation of ΣCC value.
31. (a) Schleyer, P. v. R.; Maerker, C.; Dransfeld, A.; Jiao, H.; Hommes, N. J. R. v. E. J. Am. Chem. Soc. 1996, 118, 6317.
32. To avoid the defects of NICS values, two methods are newly developed: (b) NICS(π): Schleyer, P. v. R.; Jiao, H.; Hommes, N. J. R. v. E.; Malkin, V. G.; Malkina, O. L. J. Am. Chem. Soc. 1997, 119, 12699. (c) NICS(2.0): West, R.; Buffy, J. J.; Haaf, M.; Müller, T.; Gehrhus, B.; Lappert, M. F.; Apeloig, Y. J. Am. Chem. Soc. 1998, 120, 1639.
33. To avoid the defects of NICS values, two methods are newly developed: (b) NICS(π): Schleyer, P. v. R.; Jiao, H.; Hommes, N. J. R. v. E.; Malkin, V. G.; Malkina, O. L. J. Am. Chem. Soc. 1997, 119, 12699. (c) NICS(2.0): West, R.; Buffy, J. J.; Haaf, M.; Müller, T.; Gehrhus, B.; Lappert, M. F.; Apeloig, Y. J. Am. Chem. Soc. 1998, 120, 1639.
34. (a) Bird, C. W. Tetrahedron 1985, 41, 1409.
35. (b) Bird, C. W. Tetrahedron 1986, 42, 89.
36. (c) Bird, C. W. Tetrahedron 1987, 43, 4725.
37. (d) Bird, C. W. Tetrahedron 1990, 46, 5697.
38. Nyulászi, L.; Várnai, P.; Veszprémi, T. THEOCHEM 1995, 358, 55.
39. As the distance between a three-membered ring and a measuring point becomes longer, the NICS values become smaller. The NICS values for 15 are -1.0, -0.6, -0.3, -0.2 and those for 5 are -1.1, -0.8, -0.6, -0.5 for the distances of 2.5, 3.0, 3.5, and 4.0 Å, respectively. The NICS value for 15 decreases more rapidly with increasing the distance, compared with that for 5. The origin of the abnormally large NICS(2.0) value for nonaromatic compound 15 would be ascribed to the effects of the nearby C-H σ-bonds. Three-membered aromatic compounds have larger NICS values even at the longer distances; the NICS(3.5) values for 14 and 16 are -0.4 and -0.7, respectively. Nevertheless, we can conclude from the calculations that NICS values do not always give unambiguous order of the aromaticity for three-membered ring structures at any distances.
40. 2, respectively.
41. Recently, synthesis and properties of silacalicene and germacalicene derivatives have been reported: West, R.; Sohn, H.; Apeloig, Y.; Mueller, T. In 11th International Symposium on Organosilicon Chemistry, Montpelier, France, September 1-6, 1996; Abstract LA2.
42. Fomina, L.; Sansores, L. E.; Salcedo, R. THEOCHEM 1996, 362, 257.
43. (a) Freeman, W. P.; Tilley, T. D.; Rheingold, A. L. J. Am. Chem. Soc. 1994, 116, 8428.
44. (b) Hong, J.-H.; Boudjouk, P. J. Am. Chem. Soc. 1993, 115, 5883.
45. (c) Freeman, W. P.; Tilley, T. D.; Arnold, F. P.; Rheingold, A. L.; Gantzel, P. K. Angew. Chem. Int. Ed. Engl. 1995, 34, 1887.
46. (d) Hong, J.-H.; Pan, Y.; Boudjouk, P. Angew. Chem. Int. Ed. Engl. 1996, 35, 186.
47. (a) Gordon, M. S.; Boudjouk, P.; Anwari, F. J. Am. Chem. Soc. 1983, 105, 4972.
48. (b) Damewood, I. R., Jr. J. Org. Chem. 1986, 51, 5028.
49. (c) Goldfuss, B.; Schleyer, P. v. R. Organometallics 1995, 14, 1553.
50. (d) Goldfuss, B.; Schleyer, P. v. R.; Hampel, F. Organometallics 1996, 15, 1755.
51. (e) Goldfuss, B.; Schleyer, P. v. R. Organometallics 1997, 16, 1543.
52. (a) West, R.; Sohn, H.; Powell, D. R.; Müller, T.; Apeloig, Y. Angew. Chem. Int. Ed. Engl. 1996, 35, 1002.
53. (b) West, R.; Sohn, H.; Bankwitz, U.; Calabrese, J.; Apeloig, Y.; Müller, T. J. Am. Chem. Soc. 1995, 117, 11608.
54. Nyulászi, L. J. Phys. Chem. 1996, 100, 6194.
55. (a) Nyulászi, L. J. Phys. Chem. 1995, 99, 586.
56. (b) Nyulászi, L. Inorg. Chem. 1996, 35, 4690.
57. Cloke, G. N.; Hitchcock, P. B.; Hunnable, P.; Nixon, J. F.; Nyulászi, L. Angew. Chem., Int. Ed. Engl. 1998, 37, 1083.