Novel stable silenes via a sila-Peterson-type reaction. Molecular structure and reactivity

Journal of the American Chemical Society

Volumn 118, Issue 48, 1996, Pages 12228-12229

  Apeloig, Yitzhak ^a   Bendikov, Michael ^a   Yuzefovich, Michael ^a   Nakash, Moshe ^a   Bravo Zhivotovskii, Dmitry ^a   Bläser, Dieter ^b   Boese, Roland ^b  

^a TECHNION ISRAEL INSTITUTE OF TECHNOLOGY   (Israel)

^b UNIVERSITY OF DUISBURG ESSEN   (Germany)

Author keywords

[No Author keywords available]

Indexed keywords

ORGANOSILICON DERIVATIVE;

ARTICLE; CRYSTALLOGRAPHY; DRUG SYNTHESIS; NUCLEAR MAGNETIC RESONANCE; REACTION ANALYSIS; STEREOCHEMISTRY;

EID: 0030443728     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja962844h     Document Type: Article

References (27)

1. Brook, A. G.; Abdesaken, F.; Gutekunst, B.; Gutekunst, G.; Kallury, R. K. M. J. Chem. Soc., Chem. Commun. 1981, 191.
2. For a review, see: Raabe, G.; Michl, J. In The Chemistry of Organosilicon Compounds; Patai, S., Rappoport, Z., Eds.; Wiley: Chichester, 1989; Chapter 17.
3. Wiberg, N.; Wagner, G. Angew. Chem., Int. Ed. Engl. 1983, 22, 1005.
4. Brook, A. G.; Nyburg, S. C.; Abdesaken, F.; Gutekunst, B.; Gutekunst, G.; Kallury, R. K. M. R.; Poon, Y. C.; Chang, Y.; Wong-Ng, W. J. Am. Chem. Soc. 1982, 104, 5668.
5. Wiberg, N.; Wagner, G.; Müller, G. Angew. Chem., Int. Ed. Engl. 1985, 24, 229.
6. Miracle, G. I.; Ball, J. L.; Powell, D. R.; West, R. J. Am. Chem. Soc. 1993, 115, 11598.
7. (a) Bravo-Zhivotovskii, D.; Braude, V.; Stanger, A.; Kapon, M.; Apeloig, Y. Organometallics 1992, 11, 2326
8. (b) For example, see: Luderer, F.; Reinke, H.; Oehme, H. Chem. Ber. 1996, 129, 15 and references therein.
9. 2, respectively.
10. 3SiOLi were separated. The solution was concentrated to 5 mL, and at -5°C colorless crystals of 5b, suitable for X-ray analysis, were formed.
11. 2Si), 49.7 (Si=C).
12. Gutekunst, G.; Brook, A. G. J. Organomet. Chem. 1982, 225, 1.
13. 29Si) in 2 is 144.2 ppm. See: Wiberg, N.; Wagner, G. Chem. Ber. 1986, 119, 1467.
14. 1 in 1-(trimethylsiloxy)hexene and in 1-methylhexene absorbs at 150.2 and 134.0 ppm, respectively).
15. Raabe, G.; Michl, J. Chem. Rev. 1985, 85, 419-507.
16. 4 of butadiene was also obtained in 20-30% yield.
17. 2).
18. In 1 and 2 the twisting around the C=Si bond is 14.6° and 1.6°, respectively.
19. Gutowsky, H. S.; Chen, J.; Hajduk, P. J.; Keen, J. D.; Chuang, C.; Emilsson, T. J. Am. Chem. Soc. 1991, 113, 4747.
20. GAUSSIAN 94, Revision C.2; Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Gill, P. M. W.; Johnson, B. G.; Robb, M. A.; Cheerseman, J. R.; Keith, T.; Petersson, G. A.; Montgomery, J. A.; Rahvavachari, K.; Al-Laham, M. A.; Zakrzewski, V. G.; Oritz, J. V.; Foresman, J. B.; Cioslowski, J.; Stefanov, B. B.; Nanayakkara, A.; Challacombe, M.; Peng, C. Y.; Ayala, P. Y.; Chen, W.; Wong, M. W.; Andres, J. L.; Replogle, E. S.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Binkley, J. S.; Defrees, D. J.; Baker, J.; Stewart, J. J. P.; Head-Gordon, M.; Gonzalez, C.; Pople, J. A. Gaussian, Inc.: Pittsburgh, PA, 1995.
21. 1.754 Å at MP2/6-31G* and 1.752 Å at MP4(SDQ)/6-31G* were obtained. The experimental r(C=Si) of 1.741 Å is intermediate between the RHF and the correlated values.
22. This was pointed out also for other silenes; see: (a) Apeloig, Y.; Karni, M. J. Chem. Soc., Chem. Commun. 1984, 768.
23. Apeloig, Y.; Karni, M. J. Am. Chem. Soc. 1984, 106, 6676.
24. 2, indicating that the bulky substituents in 1 have a relatively small effect on r(C=Si).
25. 2 Si: Brook, A. G.; Gajewski, J. J. Heteroat. Chem. 1990, 1, 57).
26. The reliability of these calculations is supported by the good agreement between the calculated (MMX) and the experimental structures of 5b and of the head-to-head dimer of 5a.
27. For application of this reaction to the synthesis of transient germenes, see: Bravo-Zhivotovskii, D.; Zharov, I.; Kapon, M.; Apeloig, Y. J. Chem. Soc., Chem. Commun. 1995, 1625.