Interplay of EnE′3-nC valence isomers (E, E′ = Si, Ge): Bicyclo[1.1.0]butanes with very short bridging bonds and their isomerization to alkyl-substituted cyclopropenes

Journal of the American Chemical Society

Volumn 129, Issue 9, 2007, Pages 2436-2437

  Lee, Vladimir Ya ^a   Yasuda, Hiroyuki ^a   Sekiguchi, Akira ^a  

^a UNIVERSITY OF TSUKUBA   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

ALKYL GROUP; BICYCLO COMPOUND; BICYCLO[1.1.0]BUTANE; BUTANE; GERMANIUM; SILICON; UNCLASSIFIED DRUG;

ARTICLE; CRYSTAL STRUCTURE; CYCLIZATION; GEOMETRY; ISOMER; ISOMERIZATION; STRUCTURE ANALYSIS; SYNTHESIS;

EID: 33847652881     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja068229n     Document Type: Article

References (33)

1. Woodward, R. B.; Hoffmann, R. The Conservation of Orbital Symmetry; Academic Press: New York, 1970.
2. Müller, T. In Organosilicon Chemistry IV. From Molecules to Materials; Auner, N., Weis, J., Eds.; Wiley-VCH: Weinheim, 2000, p 110.
3. Group 14 1,3- and 2,4-dienes: (a) Weidenbruch, M.; Willms, S.; Saak, W.; Henkel, G. Angew. Chem., Int. Ed. Engl. 1997, 36, 2503.
4. (b) Schäfer, H.; Saak, W.; Weidenbruch, M. Angew. Chem., Int. Ed. 2000, 39, 3703.
5. (c) Lee, V. Ya.; Ichinohe, M.; Sekiguchi, A. J. Am. Chem. Soc. 2000, 122, 12604.
6. (d) Ichinohe, M.; Sanuki, K.; Inoue, S.; Sekiguchi, A. Organometallics 2004, 23, 3088. Group 14 heavy cyclobutenes:
7. (e) Kira, M.; Iwamoto, T.; Kabuto, C. J. Am. Chem. Soc. 1996, 118, 10303.
8. (f) Wiberg, N.; Auer, H.; Nöth, H.; Knizek, J.; Polborn, K. Angew. Chem., Int. Ed. 1998, 37, 2869.
9. (g) Lee, V. Ya.; Takanashi, K.; Ichinohe, M.; Sekiguchi, A. J. Am. Chem. Soc. 2003, 125, 6012.
10. (h) Lee, V. Ya.; Takanashi, K.; Matsuno, T.; Ichinohe, M.; Sekiguchi, A. J. Am. Chem. Soc. 2004, 126, 4758. Group 14 heavy bicyclo[1.1.0]butanes:
11. (i) Fritz, G.; Wartanessian, S.; Matern, E.; Hönle, W.; Schnering, H. G. v. Z. Anorg. Allg. Chem. 1981, 475, 87.
12. (J) Masamune, S.; Kabe, Y.; Collins, S.; Williams, D. J.; Jones, R. J. Am. Chem. Soc. 1985, 107, 5552.
13. 3-cyclopropene:
14. (l) Iwamoto, T.; Kabuto, C; Kira, M. J. Am. Chem. Soc. 1999, 121, 886.
15. The formation of the Me-substituted trisilirene was recently claimed; however, neither its spectral and crystal data nor the experimental details for its synthesis have been reported: Wiberg, N.; Vasisht, S. K.; Fischer, G.; Mayer, P. Z. Anorg. Allg. Chem. 2004, 630, 1823.
16. Sekiguchi, A.; Lee, V. Ya. Chem. Rev. 2003, 103, 1429.
17. Lee, V. Ya.; Yasuda, H.; Ichinohe, M.; Sekiguchi, A. Angew. Chem., Int. Ed. 2005, 44, 6378.
18. For the experimental procedures and spectral data of 7 and 8 and crystal data of 7a see Supporting Information.
19. (a) Power, P. P. Chem. Rev. 1999, 99, 3463.
20. (b) See also ref. 5.
21. Sekiguchi, A.; Inoue, S.; Ichinohe, M.; Arai, Y. J. Am. Chem. Soc. 2004, 126, 9626.
22. (a) Budzelaar, P. H. M.; Kraka, E.; Cremer, D.; Schleyer, P. v. R. J. Am. Chem. Soc. 1986, 108, 561.
23. (b) Schoeller, W. W.; Dabisch, T.; Busch, T. Inorg. Chem. 1987, 26, 4383.
24. Masamune, S.; Murakami, S.; Tobita, H.; Williams, D. J. J. Am. Chem. Soc. 1983, 105, 7776.
25. b Å, respectively:
26. (a) Boatz, J. A.; Gordon, M. S. J. Phys. Chem. 1988, 92, 3037.
27. (b) Kitchen, D. B.; Jackson, J. E.; Allen, L. C. J. Am. Chem. Soc. 1990, 112, 3408.
28. The HOMO of 7a is represented by the bonding combination of the highly bent orbitals of the bridgehead Si atoms, directed approximately midway between the horizontal (σ-type) and vertical (π-type) overlap (GAUSSIAN 98 at the B3LYP/6-31G(d) level).
29. The detailed description of the nature of Si-Si bridging bond in 7a,b, as well as the mechanism of thermal isomerization of 7 to 8 (kinetics, trapping reactions) will be discussed in the forthcoming full paper.
30. Examples of interconversions between the heavy cyclobutenes, bicyclo[1.1.0]butanes and cyclopropenes, have been recently reported:
31. (a) ref. 3e.
32. (b) Iwamoto, T.; Kira, M. Chem. Lett. 1998, 277.
33. (c) Iwamoto, T.; Tamura, M.; Kabuto, C.; Kira, M. Organometallics 2003, 22, 2342.