A mechanistic investigation of the carbon-carbon bond cleavage of aryl and alkyl cyanides using a cationic Rh(III) silyl complex

Journal of the American Chemical Society

Volumn 125, Issue 32, 2003, Pages 9808-9813

  Taw, Felicia L ^a   Mueller, Alexander H ^a   Bergman, Robert G ^b   Brookhart, Maurice ^a  

^a University of North Carolina at Chapel Hill   (United States)

^b UNIVERSITY OF CALIFORNIA   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CARBON; CRYSTAL STRUCTURE; CYANIDES; POSITIVE IONS; REACTION KINETICS; X RAY ANALYSIS;

CARBON-CARBON BOND;

CHEMICAL BONDS;

4 METHOXYBENZONITRILE; BENZONITRILE; CARBON; CYANIDE; RHODIUM; SILICON DERIVATIVE; UNCLASSIFIED DRUG;

ARTICLE; CHEMICAL BOND; CRYSTAL STRUCTURE; KINETICS; TEMPERATURE; X RAY CRYSTALLOGRAPHY;

EID: 0042626231     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja034468o     Document Type: Article

References (34)

1. (a) Jun, C. H.; Moon, C. W.; Lee, D. Y. Chem.-Eur. J. 2002, 8, 2422.
2. (b) Müller, C.; Lachicotte, R. J.; Jones, W. D. Organometallics 2002, 21, 1975.
3. (c) Rybtchinski, B.; Milstein, D. Angew. Chem., Int. Ed. 1999, 38, 870.
4. (d) Murakami, M.; Ito, Y. In Topics in Organometallic Chemistry; Murai, S., Ed.: Springer-Verlag: New York, 1999.
5. (e) Crabtree, R. H. Chem. Rev. 1985, 85, 245.
6. Churchill, D.; Shin, J. H.; Hascall, T.; Hahn, J. M.; Bridgewater. B. M. ; Parkin, G. Organometallics 1999, 18, 2403.
7. For examples, see: (a) Miller, J. A. Tetrahedron Lett. 2001, 6991.
8. (b) Abla, M.; Yamamoto, T. J. Organomet. Chem. 1997, 532, 267.
9. (c) Favero, G.; Morvillo, A.; Turco, A. J. Organomet. Chem. 1983, 241, 251.
10. (d) Parshall, G. W. J. Am. Chem. Soc. 1974, 96, 2360.
11. (e) Gerlach, D. H.; Kane, A. R.; Parshall, G. W.; Jesson, J. P.; Muetterties, E. L. J. Am. Chem. Soc. 1971, 93, 3543.
12. (a) Garcia, J. J.; Jones, W. D. Organometallics 2000, 19, 5544.
13. (b) Garcia, J. J.; Brunkan, N. M.; Jones, W. D. J. Am. Chem. Soc. 2002, 124, 9547.
14. Taw, F. L.; White, P. S.; Bergman, R. G.; Brookhart, M. J. Am. Chem. Soc. 2002, 124, 4192.
15. Taw, F. L.; Mellows, H.; White, P. S.; Hollander, F. J.; Bergman, R. G.; Brookhart, M.; Heinekey, D. M. J. Am. Chem. Soc. 2002, 124, 5100.
16. Taw, F. L.; Bergman, R. G.; Brookhart, M., unpublished results.
17. Complete spectroscopic data have been reported for complexes 1-8 in the Supporting Information of ref 5.
18. P-C = 6.9 Hz.
19. Rh-P = 177.2 Hz).
20. For a few representative examples, see: (a) Shin, J. H.; Savage, W.; Murphy, V. J.; Bonanno, J. B.; Churchill, D. G.; Parkin, G. J. Chem. Soc., Dalton Trans. 2001, 11, 1732. (b) Sánchez-Nieves, J.; Royo, P.; Pellinghelli, M. A.; Tiripicchio, A. Organometallics 2000, 19, 3161. (c) Wu, Z. ; Diminnie, J. B.; Xue, Z. Organometallics 1999, 18, 1002. (d) Daff, P. J.; Monge, A.; Palma, P.; Poveda, M. L.; Ruiz, C.; Valerga, P.; Carmona, E. Organometallics 1997, 16, 2263. (e) Bochmann, M.; Wilson, L. M.; Hursthouse, M. B.; Motevalli, M. Organometallics 1988, 7, 1148. (f) Chetcuti, P. A.; Knobler, C. B.; Hursthouse, M. F. Organometallics 1988, 7, 650. (g) Campion, B. K.; Falk, J.; Tilley, T. D. J. Am. Chem. Soc. 1987, 109, 2049.
21. For a few representative examples, see: (a) Shin, J. H.; Savage, W.; Murphy, V. J.; Bonanno, J. B.; Churchill, D. G.; Parkin, G. J. Chem. Soc., Dalton Trans. 2001, 11, 1732. (b) Sánchez-Nieves, J.; Royo, P.; Pellinghelli, M. A.; Tiripicchio, A. Organometallics 2000, 19, 3161. (c) Wu, Z. ; Diminnie, J. B.; Xue, Z. Organometallics 1999, 18, 1002. (d) Daff, P. J.; Monge, A.; Palma, P.; Poveda, M. L.; Ruiz, C.; Valerga, P.; Carmona, E. Organometallics 1997, 16, 2263. (e) Bochmann, M.; Wilson, L. M.; Hursthouse, M. B.; Motevalli, M. Organometallics 1988, 7, 1148. (f) Chetcuti, P. A.; Knobler, C. B.; Hursthouse, M. F. Organometallics 1988, 7, 650. (g) Campion, B. K.; Falk, J.; Tilley, T. D. J. Am. Chem. Soc. 1987, 109, 2049.
22. For a few representative examples, see: (a) Shin, J. H.; Savage, W.; Murphy, V. J.; Bonanno, J. B.; Churchill, D. G.; Parkin, G. J. Chem. Soc., Dalton Trans. 2001, 11, 1732. (b) Sánchez-Nieves, J.; Royo, P.; Pellinghelli, M. A.; Tiripicchio, A. Organometallics 2000, 19, 3161. (c) Wu, Z. ; Diminnie, J. B.; Xue, Z. Organometallics 1999, 18, 1002. (d) Daff, P. J.; Monge, A.; Palma, P.; Poveda, M. L.; Ruiz, C.; Valerga, P.; Carmona, E. Organometallics 1997, 16, 2263. (e) Bochmann, M.; Wilson, L. M.; Hursthouse, M. B.; Motevalli, M. Organometallics 1988, 7, 1148. (f) Chetcuti, P. A.; Knobler, C. B.; Hursthouse, M. F. Organometallics 1988, 7, 650. (g) Campion, B. K.; Falk, J.; Tilley, T. D. J. Am. Chem. Soc. 1987, 109, 2049.
23. For a few representative examples, see: (a) Shin, J. H.; Savage, W.; Murphy, V. J.; Bonanno, J. B.; Churchill, D. G.; Parkin, G. J. Chem. Soc., Dalton Trans. 2001, 11, 1732. (b) Sánchez-Nieves, J.; Royo, P.; Pellinghelli, M. A.; Tiripicchio, A. Organometallics 2000, 19, 3161. (c) Wu, Z. ; Diminnie, J. B.; Xue, Z. Organometallics 1999, 18, 1002. (d) Daff, P. J.; Monge, A.; Palma, P.; Poveda, M. L.; Ruiz, C.; Valerga, P.; Carmona, E. Organometallics 1997, 16, 2263. (e) Bochmann, M.; Wilson, L. M.; Hursthouse, M. B.; Motevalli, M. Organometallics 1988, 7, 1148. (f) Chetcuti, P. A.; Knobler, C. B.; Hursthouse, M. F. Organometallics 1988, 7, 650. (g) Campion, B. K.; Falk, J.; Tilley, T. D. J. Am. Chem. Soc. 1987, 109, 2049.
24. For a few representative examples, see: (a) Shin, J. H.; Savage, W.; Murphy, V. J.; Bonanno, J. B.; Churchill, D. G.; Parkin, G. J. Chem. Soc., Dalton Trans. 2001, 11, 1732. (b) Sánchez-Nieves, J.; Royo, P.; Pellinghelli, M. A.; Tiripicchio, A. Organometallics 2000, 19, 3161. (c) Wu, Z. ; Diminnie, J. B.; Xue, Z. Organometallics 1999, 18, 1002. (d) Daff, P. J.; Monge, A.; Palma, P.; Poveda, M. L.; Ruiz, C.; Valerga, P.; Carmona, E. Organometallics 1997, 16, 2263. (e) Bochmann, M.; Wilson, L. M.; Hursthouse, M. B.; Motevalli, M. Organometallics 1988, 7, 1148. (f) Chetcuti, P. A.; Knobler, C. B.; Hursthouse, M. F. Organometallics 1988, 7, 650. (g) Campion, B. K.; Falk, J.; Tilley, T. D. J. Am. Chem. Soc. 1987, 109, 2049.
25. For a few representative examples, see: (a) Shin, J. H.; Savage, W.; Murphy, V. J.; Bonanno, J. B.; Churchill, D. G.; Parkin, G. J. Chem. Soc., Dalton Trans. 2001, 11, 1732. (b) Sánchez-Nieves, J.; Royo, P.; Pellinghelli, M. A.; Tiripicchio, A. Organometallics 2000, 19, 3161. (c) Wu, Z. ; Diminnie, J. B.; Xue, Z. Organometallics 1999, 18, 1002. (d) Daff, P. J.; Monge, A.; Palma, P.; Poveda, M. L.; Ruiz, C.; Valerga, P.; Carmona, E. Organometallics 1997, 16, 2263. (e) Bochmann, M.; Wilson, L. M.; Hursthouse, M. B.; Motevalli, M. Organometallics 1988, 7, 1148. (f) Chetcuti, P. A.; Knobler, C. B.; Hursthouse, M. F. Organometallics 1988, 7, 650. (g) Campion, B. K.; Falk, J.; Tilley, T. D. J. Am. Chem. Soc. 1987, 109, 2049.
26. For a few representative examples, see: (a) Shin, J. H.; Savage, W.; Murphy, V. J.; Bonanno, J. B.; Churchill, D. G.; Parkin, G. J. Chem. Soc., Dalton Trans. 2001, 11, 1732. (b) Sánchez-Nieves, J.; Royo, P.; Pellinghelli, M. A.; Tiripicchio, A. Organometallics 2000, 19, 3161. (c) Wu, Z. ; Diminnie, J. B.; Xue, Z. Organometallics 1999, 18, 1002. (d) Daff, P. J.; Monge, A.; Palma, P.; Poveda, M. L.; Ruiz, C.; Valerga, P.; Carmona, E. Organometallics 1997, 16, 2263. (e) Bochmann, M.; Wilson, L. M.; Hursthouse, M. B.; Motevalli, M. Organometallics 1988, 7, 1148. (f) Chetcuti, P. A.; Knobler, C. B.; Hursthouse, M. F. Organometallics 1988, 7, 650. (g) Campion, B. K.; Falk, J.; Tilley, T. D. J. Am. Chem. Soc. 1987, 109, 2049.
27. 1). This is clearly the case for 4-methoxybenzonitrile because the intermediate (complex 11) builds up to over 90%. We assume this assumption is valid for the other aryl nitriles.
28. Connors, K. A. Chemical Kinetics; VCH Publishers: New York, 1990.
29. (a) Axe, F. U.; Marynick, D. S. J. Am. Chem. Soc. 1988, 110, 3728.
30. (b) Cotton, J. D.; Markwell, R. D. J. Organomet. Chem. 1990, 388, 123.
31. (c) Clark, G. R.; Roper, W. R.; Wright, L. J.; Yap, V. P. D. Organometallics 1997, 16, 5135.
32. (a) Pangborn, A. B.; Giardello, M. A.; Grubbs, R. H.; Rosen, R. K.; Timmers, F. J. Organometallics 1996, 15, 1518.
33. (b) Alaimo, P. J.; Peters, D. W.; Arnold, J.; Bergman, R. G. J. Chem. Educ. 2001, 78, 64.
34. Gabe, E. J.; Le Page, Y.; Charland, J.-P.; Lee, F. L.; White, P. S. J. Appl. Crystallogr. 1989, 22, 384.