The first isolable dialkylsilylene [1]

Journal of the American Chemical Society

Volumn 121, Issue 41, 1999, Pages 9722-9723

  Kira, Mitsuo ^a   Ishida, Shintaro ^a   Iwamoto, Takeaki ^a   Kabuto, Chizuko ^a  

^a TOHOKU UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

SILICON DERIVATIVE;

CHEMICAL ANALYSIS; CHEMICAL BINDING; CHEMICAL STRUCTURE; LETTER; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; STRUCTURE ANALYSIS; X RAY DIFFRACTION;

EID: 0032732193     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja9925305     Document Type: Letter

References (49)

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13. For reviews of stable cyclic diaminosilylenes, see: (a) West, R.; Denk, M. Pure Appl. Chem. 1996, 68, 785. (b) Denk, M.; West, R.; Hayashi, R.; Apeloig, Y.; Pauncz, R.; Karni, M. In Organosilicon Chemistry II; Auner, N., Weis, J., Eds.; VCH: Weinheim, Germany, 1996; pp 251-261. (c) Weidenbruch, M. Eur. J. Inorg. Chem. 1999, 373. (d) Driess, M.; Grützmacher, H. Angew. Chem., Int. Ed. Engl. 1996, 35, 828. (e) Gehrhus, B.; Lappert, M. F. Phosphorus, Sulfur Silicon Relat. Elem. 1997, 124 & 125, 537.
14. For reviews of stable cyclic diaminosilylenes, see: (a) West, R.; Denk, M. Pure Appl. Chem. 1996, 68, 785. (b) Denk, M.; West, R.; Hayashi, R.; Apeloig, Y.; Pauncz, R.; Karni, M. In Organosilicon Chemistry II; Auner, N., Weis, J., Eds.; VCH: Weinheim, Germany, 1996; pp 251-261. (c) Weidenbruch, M. Eur. J. Inorg. Chem. 1999, 373. (d) Driess, M.; Grützmacher, H. Angew. Chem., Int. Ed. Engl. 1996, 35, 828. (e) Gehrhus, B.; Lappert, M. F. Phosphorus, Sulfur Silicon Relat. Elem. 1997, 124 & 125, 537.
15. For reviews of stable cyclic diaminosilylenes, see: (a) West, R.; Denk, M. Pure Appl. Chem. 1996, 68, 785. (b) Denk, M.; West, R.; Hayashi, R.; Apeloig, Y.; Pauncz, R.; Karni, M. In Organosilicon Chemistry II; Auner, N., Weis, J., Eds.; VCH: Weinheim, Germany, 1996; pp 251-261. (c) Weidenbruch, M. Eur. J. Inorg. Chem. 1999, 373. (d) Driess, M.; Grützmacher, H. Angew. Chem., Int. Ed. Engl. 1996, 35, 828. (e) Gehrhus, B.; Lappert, M. F. Phosphorus, Sulfur Silicon Relat. Elem. 1997, 124 & 125, 537.
16. For reviews of stable cyclic diaminosilylenes, see: (a) West, R.; Denk, M. Pure Appl. Chem. 1996, 68, 785. (b) Denk, M.; West, R.; Hayashi, R.; Apeloig, Y.; Pauncz, R.; Karni, M. In Organosilicon Chemistry II; Auner, N., Weis, J., Eds.; VCH: Weinheim, Germany, 1996; pp 251-261. (c) Weidenbruch, M. Eur. J. Inorg. Chem. 1999, 373. (d) Driess, M.; Grützmacher, H. Angew. Chem., Int. Ed. Engl. 1996, 35, 828. (e) Gehrhus, B.; Lappert, M. F. Phosphorus, Sulfur Silicon Relat. Elem. 1997, 124 & 125, 537.
17. For reviews of stable cyclic diaminosilylenes, see: (a) West, R.; Denk, M. Pure Appl. Chem. 1996, 68, 785. (b) Denk, M.; West, R.; Hayashi, R.; Apeloig, Y.; Pauncz, R.; Karni, M. In Organosilicon Chemistry II; Auner, N., Weis, J., Eds.; VCH: Weinheim, Germany, 1996; pp 251-261. (c) Weidenbruch, M. Eur. J. Inorg. Chem. 1999, 373. (d) Driess, M.; Grützmacher, H. Angew. Chem., Int. Ed. Engl. 1996, 35, 828. (e) Gehrhus, B.; Lappert, M. F. Phosphorus, Sulfur Silicon Relat. Elem. 1997, 124 & 125, 537.
18. For reviews on stable carbenes, see: (a) Arduengo, A. J., III.; Krafczyk, R. Chem.-Ztg. 1998, 32, 6. (b) Bertrand, G.; Reed, R. Coord. Chem. Rev. 1994, 137, 323. (c) Herrmann, W. A.; Köcher, C. Angew. Chem., Int. Ed. Engl. 1997, 56, 2162.
19. For reviews on stable carbenes, see: (a) Arduengo, A. J., III.; Krafczyk, R. Chem.-Ztg. 1998, 32, 6. (b) Bertrand, G.; Reed, R. Coord. Chem. Rev. 1994, 137, 323. (c) Herrmann, W. A.; Köcher, C. Angew. Chem., Int. Ed. Engl. 1997, 56, 2162.
20. For reviews on stable carbenes, see: (a) Arduengo, A. J., III.; Krafczyk, R. Chem.-Ztg. 1998, 32, 6. (b) Bertrand, G.; Reed, R. Coord. Chem. Rev. 1994, 137, 323. (c) Herrmann, W. A.; Köcher, C. Angew. Chem., Int. Ed. Engl. 1997, 56, 2162.
21. The electronic nature of heteroatom-substituted carbenes and silylenes remains a controversial topic. (a) Dixon, D. A.; Dobbs, K. B.; Arduengo, A. J., III.; Bertrand, G. J. Am. Chem. Soc. 1991, 113, 8782. (b) Dagani, R. Chem. Eng. News 1991, 69 (4), 19. (c) Regitz, M. Angew. Chem., Int. Ed. Engl. 1991, 30, 674. (d) Dagani, R. Chem. Eng. News 1994, 72 (18), 20. (e) Heinemann, C.; Müller, T.; Apeloig, Y.; Schwartz, H. J. Am. Chem. Soc. 1996, 118, 2023. (f) Boehme, C.; Frenking, G. J. Am. Chem. Soc. 1996, 118, 2039. (g) Veszprémi, T.; Nyulászi, L.; Hajgato, B.; Heinicke, J. THEOCHEM 1998, 431, 1. (h) West, R.; Buffy, J. J.; Haaf, M.; Müller, T.; Gehrhus, B.; Lappert, M. F.; Apeloig, Y. J. Am. Chem. Soc. 1998, 120, 1639.
22. The electronic nature of heteroatom-substituted carbenes and silylenes remains a controversial topic. (a) Dixon, D. A.; Dobbs, K. B.; Arduengo, A. J., III.; Bertrand, G. J. Am. Chem. Soc. 1991, 113, 8782. (b) Dagani, R. Chem. Eng. News 1991, 69 (4), 19. (c) Regitz, M. Angew. Chem., Int. Ed. Engl. 1991, 30, 674. (d) Dagani, R. Chem. Eng. News 1994, 72 (18), 20. (e) Heinemann, C.; Müller, T.; Apeloig, Y.; Schwartz, H. J. Am. Chem. Soc. 1996, 118, 2023. (f) Boehme, C.; Frenking, G. J. Am. Chem. Soc. 1996, 118, 2039. (g) Veszprémi, T.; Nyulászi, L.; Hajgato, B.; Heinicke, J. THEOCHEM 1998, 431, 1. (h) West, R.; Buffy, J. J.; Haaf, M.; Müller, T.; Gehrhus, B.; Lappert, M. F.; Apeloig, Y. J. Am. Chem. Soc. 1998, 120, 1639.
23. The electronic nature of heteroatom-substituted carbenes and silylenes remains a controversial topic. (a) Dixon, D. A.; Dobbs, K. B.; Arduengo, A. J., III.; Bertrand, G. J. Am. Chem. Soc. 1991, 113, 8782. (b) Dagani, R. Chem. Eng. News 1991, 69 (4), 19. (c) Regitz, M. Angew. Chem., Int. Ed. Engl. 1991, 30, 674. (d) Dagani, R. Chem. Eng. News 1994, 72 (18), 20. (e) Heinemann, C.; Müller, T.; Apeloig, Y.; Schwartz, H. J. Am. Chem. Soc. 1996, 118, 2023. (f) Boehme, C.; Frenking, G. J. Am. Chem. Soc. 1996, 118, 2039. (g) Veszprémi, T.; Nyulászi, L.; Hajgato, B.; Heinicke, J. THEOCHEM 1998, 431, 1. (h) West, R.; Buffy, J. J.; Haaf, M.; Müller, T.; Gehrhus, B.; Lappert, M. F.; Apeloig, Y. J. Am. Chem. Soc. 1998, 120, 1639.
24. The electronic nature of heteroatom-substituted carbenes and silylenes remains a controversial topic. (a) Dixon, D. A.; Dobbs, K. B.; Arduengo, A. J., III.; Bertrand, G. J. Am. Chem. Soc. 1991, 113, 8782. (b) Dagani, R. Chem. Eng. News 1991, 69 (4), 19. (c) Regitz, M. Angew. Chem., Int. Ed. Engl. 1991, 30, 674. (d) Dagani, R. Chem. Eng. News 1994, 72 (18), 20. (e) Heinemann, C.; Müller, T.; Apeloig, Y.; Schwartz, H. J. Am. Chem. Soc. 1996, 118, 2023. (f) Boehme, C.; Frenking, G. J. Am. Chem. Soc. 1996, 118, 2039. (g) Veszprémi, T.; Nyulászi, L.; Hajgato, B.; Heinicke, J. THEOCHEM 1998, 431, 1. (h) West, R.; Buffy, J. J.; Haaf, M.; Müller, T.; Gehrhus, B.; Lappert, M. F.; Apeloig, Y. J. Am. Chem. Soc. 1998, 120, 1639.
25. The electronic nature of heteroatom-substituted carbenes and silylenes remains a controversial topic. (a) Dixon, D. A.; Dobbs, K. B.; Arduengo, A. J., III.; Bertrand, G. J. Am. Chem. Soc. 1991, 113, 8782. (b) Dagani, R. Chem. Eng. News 1991, 69 (4), 19. (c) Regitz, M. Angew. Chem., Int. Ed. Engl. 1991, 30, 674. (d) Dagani, R. Chem. Eng. News 1994, 72 (18), 20. (e) Heinemann, C.; Müller, T.; Apeloig, Y.; Schwartz, H. J. Am. Chem. Soc. 1996, 118, 2023. (f) Boehme, C.; Frenking, G. J. Am. Chem. Soc. 1996, 118, 2039. (g) Veszprémi, T.; Nyulászi, L.; Hajgato, B.; Heinicke, J. THEOCHEM 1998, 431, 1. (h) West, R.; Buffy, J. J.; Haaf, M.; Müller, T.; Gehrhus, B.; Lappert, M. F.; Apeloig, Y. J. Am. Chem. Soc. 1998, 120, 1639.
26. The electronic nature of heteroatom-substituted carbenes and silylenes remains a controversial topic. (a) Dixon, D. A.; Dobbs, K. B.; Arduengo, A. J., III.; Bertrand, G. J. Am. Chem. Soc. 1991, 113, 8782. (b) Dagani, R. Chem. Eng. News 1991, 69 (4), 19. (c) Regitz, M. Angew. Chem., Int. Ed. Engl. 1991, 30, 674. (d) Dagani, R. Chem. Eng. News 1994, 72 (18), 20. (e) Heinemann, C.; Müller, T.; Apeloig, Y.; Schwartz, H. J. Am. Chem. Soc. 1996, 118, 2023. (f) Boehme, C.; Frenking, G. J. Am. Chem. Soc. 1996, 118, 2039. (g) Veszprémi, T.; Nyulászi, L.; Hajgato, B.; Heinicke, J. THEOCHEM 1998, 431, 1. (h) West, R.; Buffy, J. J.; Haaf, M.; Müller, T.; Gehrhus, B.; Lappert, M. F.; Apeloig, Y. J. Am. Chem. Soc. 1998, 120, 1639.
27. The electronic nature of heteroatom-substituted carbenes and silylenes remains a controversial topic. (a) Dixon, D. A.; Dobbs, K. B.; Arduengo, A. J., III.; Bertrand, G. J. Am. Chem. Soc. 1991, 113, 8782. (b) Dagani, R. Chem. Eng. News 1991, 69 (4), 19. (c) Regitz, M. Angew. Chem., Int. Ed. Engl. 1991, 30, 674. (d) Dagani, R. Chem. Eng. News 1994, 72 (18), 20. (e) Heinemann, C.; Müller, T.; Apeloig, Y.; Schwartz, H. J. Am. Chem. Soc. 1996, 118, 2023. (f) Boehme, C.; Frenking, G. J. Am. Chem. Soc. 1996, 118, 2039. (g) Veszprémi, T.; Nyulászi, L.; Hajgato, B.; Heinicke, J. THEOCHEM 1998, 431, 1. (h) West, R.; Buffy, J. J.; Haaf, M.; Müller, T.; Gehrhus, B.; Lappert, M. F.; Apeloig, Y. J. Am. Chem. Soc. 1998, 120, 1639.
28. The electronic nature of heteroatom-substituted carbenes and silylenes remains a controversial topic. (a) Dixon, D. A.; Dobbs, K. B.; Arduengo, A. J., III.; Bertrand, G. J. Am. Chem. Soc. 1991, 113, 8782. (b) Dagani, R. Chem. Eng. News 1991, 69 (4), 19. (c) Regitz, M. Angew. Chem., Int. Ed. Engl. 1991, 30, 674. (d) Dagani, R. Chem. Eng. News 1994, 72 (18), 20. (e) Heinemann, C.; Müller, T.; Apeloig, Y.; Schwartz, H. J. Am. Chem. Soc. 1996, 118, 2023. (f) Boehme, C.; Frenking, G. J. Am. Chem. Soc. 1996, 118, 2039. (g) Veszprémi, T.; Nyulászi, L.; Hajgato, B.; Heinicke, J. THEOCHEM 1998, 431, 1. (h) West, R.; Buffy, J. J.; Haaf, M.; Müller, T.; Gehrhus, B.; Lappert, M. F.; Apeloig, Y. J. Am. Chem. Soc. 1998, 120, 1639.
29. 5, 372.1977; found, 372.1967.
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31. w = 0.036.
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39. 2
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44. max/nm (∈) 338 (∼9000).
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46. Theoretically, the isomerization of silylmethylsilylene to 1-silylsilaethene is predicted to occur more facilely than the isomerization of methylsilylene to silaethene. Nagase, S.; Kudo, T. J. Chem. Soc., Chem. Commun. 1984, 1392. See also: Apeloig, Y. In The Chemistry of Organic Silicon Compounds; Patai, S., Rappoport, Z., Eds.; John Wiley & Sons: New York, 1989; Part 1, Chapter 2, pp 57-225.
47. Theoretically, the isomerization of silylmethylsilylene to 1-silylsilaethene is predicted to occur more facilely than the isomerization of methylsilylene to silaethene. Nagase, S.; Kudo, T. J. Chem. Soc., Chem. Commun. 1984, 1392. See also: Apeloig, Y. In The Chemistry of Organic Silicon Compounds; Patai, S., Rappoport, Z., Eds.; John Wiley & Sons: New York, 1989; Part 1, Chapter 2, pp 57-225.
48. The inverse isomerization from a 1-silylsilaethene to the corresponding silylmethylsilylene at high temperatures in the gas phase has been reported. Barton, T. J.; Burns, S. A.; Burns, G. T. Organometallics 1982, 1, 210.
49. A mechanistic study of the isomerization is in progress. As suggested by a reviewer, the isomerization of 1 to 8 may not occur by an intramolecular 1,2-silyl migration but by an intermolecular process as recently reported in the N-heterocyclic carbene series: Solé, S.; Gornitzka, H.; Gurret, O.; Bertrand, G. J. Am. Chem. Soc. 1998, 120, 9100.