Tri-tert-butylsilylsilylenes with alkali metal substituents ( tBu3Si)SiM (M = Li, K): Electronically and sterically accessible triplet ground states

Journal of the American Chemical Society

Volumn 130, Issue 2, 2008, Pages 426-427

  Sekiguchi, Akira ^a   Tanaka, Takashi ^a   Ichinohe, Masaaki ^a   Akiyama, Kimio ^b   Gaspar, Peter P ^c  

^a UNIVERSITY OF TSUKUBA   (Japan)

^b TOHOKU UNIVERSITY   (Japan)

^c WASHINGTON UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALKALI; LITHIUM; POTASSIUM; SILANE DERIVATIVE;

ARTICLE; ELECTROCHEMISTRY; IRRADIATION; MATHEMATICAL MODEL; MOLECULAR INTERACTION; NUCLEAR MAGNETIC RESONANCE; PHOTOLYSIS;

EID: 41449090400     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja077628v     Document Type: Article

References (18)

1. For reviews, see: (a) Apeloig, Y. In The Chemistry of Organic Silicon Compounds; Patai, S., Rappoport, Z., Eds.; John Wiley & Sons Ltd.: New York, 1989; Part 1, Chapter 2.
2. (b) Gaspar, P. P.; West, R. In The Chemistry of Organic Silicon Compounds II; Rappoport, Z., Apeloig, Y., Eds.; John Wiley & Sons Ltd.: New York, 1998; Vol. 2, Part 3, Chapter 43.
3. (c) Gaspar, P. P.; Xiao, M.; Pae, D. H.; Berger, D. J.; Haile, T.; Chen, T.; Lei, D.; Winchester, W. R.; Jiang, P. J. Organomet. Chem. 2002, 646, 68.
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7. Jiang, P.; Gaspar, P. P. J. Am. Chem. Soc. 2001, 123, 8622. This interpretation is under question on the basis of quantum mechanical calculations: Apeloig, Y. private communication.
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9. (b) Colvin, M. E.; Breulet, J.; Schaefer, H. F., III. Tetrahedron 1985, 41, 1429.
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11. The silacyclopropenyllithium 2a was independently prepared by the reaction of 1-bromo-2,3-diethyl-1-(tri-tert-butylsilyl)-1-silacycloprop- 2-ene with lithium in THF. Tanaka, T.; Ichinohe, M.; Sekiguchi, A. Chem. Lett. 2004, 33, 1420.
12. For the experimental procedure and spectral data, see Supporting Information.
13. The EPR signal observed at 340 mT corresponds to a typical silyl radical, but its structure is unclear at this moment.
14. Li, X.; Weissman, S. I.; Lin, T.-S.; Gaspar, P. P.; Cowley, A. H.; Smirnov, A. I. J. Am. Chem. Soc. 1994, 116, 7899.
15. For the computational results, see Supporting Information.
16. For the experimental studies on the interaction of singlet silylenes with Lewis bases, see: (a) Gillette, G. R.; Noren, G. H.; West, R. Organometallics 1987, 6, 2617.
17. (b) Ando, W.; Sekiguchi, A.; Hagiwara, K.; Sakakibara, A.; Yoshida, H. Organometallics 1988, 7, 558.
18. 2 (n = 0-3) are calculated to be -3.2, -1.0, 6.4, and 8.9 kcal/mol, respectively.