Radical reactions of a stable N-hetorocyclic silylene: EPR study and DFT calculation

Journal of the American Chemical Society

Volumn 126, Issue 25, 2004, Pages 7786-7787

  Tumanskii, Boris ^a   Pine, Pauline ^a   Apeloig, Yitzhak ^a   Hill, Nicholas J ^b   West, Robert ^b  

^a TECHNION ISRAEL INSTITUTE OF TECHNOLOGY   (Israel)

^b UNIVERSITY OF WISCONSIN MADISON   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

HETEROCYCLIC NITRO COMPOUND; RADICAL; SILICON DERIVATIVE; SILYLENE; UNCLASSIFIED DRUG;

ACCELERATION; ARTICLE; CONFORMATION; DENSITY; DENSITY FUNCTIONAL THEORY; ELECTRON SPIN RESONANCE; MOLECULAR STABILITY; QUANTUM MECHANICS; RADICAL REACTION;

EID: 3042687905     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja049114r     Document Type: Article

References (14)

1. Gaspar, P. P.; West, R. In Rappoport, Z., Apeloig, Y., Eds. The Chemistry of Organic Silicon Compounds; Wiley: New York, 1998; Vol. 2, Part 3, Chapter 43.
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3. Haaf, M.; Schmedake, T. A.; West, R. Acc. Chem. Res. 2000, 33, 704.
4. Avent, A. G.; Gehrhus, B.; Hitchcock, P. B.; Lappert, M. F.; Maciejewski, H. J. Organometallics. Chem. 2003, 686, 321.
5. Amoroso, D.; Haaf, M.; Yap, G. P. A.; West, R.; Fogg, D. E. Organometallics 2002, 21, 534.
6. Haaf, M.; Schmedake, T. A.; Paradise, B.; J.; Millevolte, A. J.; Powell, D. R.; West, R. J. Organomet. Chem. 2001, 636, 17.
7. (a) Davies, A. G.; Dennis, R. W.; Roberts, B. P. J. Chem. Soc., Perkin II 1974, 1101
8. (b) Dennis, R. W.; Roberts, B. P. J. Chem. Soc., Perkin II 1975, 140
9. (c) Bentrude, W. G.; Min, T. B. J. Am. Chem. Soc. 1972, 94, 1025,
10. Reaction of a stable silylene with TEMPO has recently been reported without identification of a radical intermediate (which would not be stabilized by delocalization): Iwamoto, T.; Masuda, H.; Ishida, S.; Kabuto, C.; Kira, M. J. Am. Chem. Soc. 2003, 125. 9300.
11. Hudson, A.; Lappert, M. F.; Lednor, P. W.; Nicholson, B. K. J. Chem. Soc., Chem. Commun. 1974, 966.
12. 5] We suppose that the initially formed radicals react with toluene to form benzyl radicals, which then add to the silylene radical to produce 12. The hfc constants for radical 12 differ somewhat from those for the other radicals reported here, perhaps due to different pyramidality at silicon.
13. Wertz J. E.; Bolton, J. R. Electron Spin Resonance; McGraw-Hill Book Company: New York, 1972; Chapter 9.
14. For details of the calculations see the Supporting Information.