Well-defined ruthenium olefin metathesis catalysts: Mechanism and activity

Journal of the American Chemical Society

Volumn 119, Issue 17, 1997, Pages 3887-3897

  Dias, Eric L ^a   Nguyen, SonBinh T ^a   Grubbs, Robert H ^a  

^a California Institute of Technology ^*  (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALKADIENE; ALKENE DERIVATIVE; COPPER CHLORIDE; HALOGEN; LIGAND; MALONIC ACID DERIVATIVE; PHOSPHINE DERIVATIVE; RUTHENIUM;

ARTICLE; CATALYST; CHEMICAL REACTION KINETICS; LIGAND BINDING; REACTION ANALYSIS; STEREOCHEMISTRY; SYNTHESIS;

EID: 0030994105     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja963136z     Document Type: Article

References (38)

1. Nguyen, S. T.; Johnson, L. K.; Grubbs, R. H. J. Am. Chem. Soc. 1992, 114, 3974-3975.
2. Wu, Z.; Benedicto, A. D.; Grubbs, R. H. Macromolecules 1993, 26, 4975-4977.
3. Wu, Z.; Nguyen, S. T.; Grubbs, R. H.; Ziller, J. W. J. Am. Chem. Soc. 1995, 117, 5503-5511.
4. Nguyen, S. T.; Grubbs, R. H.; Ziller, J. W. J. Am. Chem. Soc. 1993, 115, 9858-9859.
5. Hillmyer, M. A.; Laredo, W. R.; Grubbs, R. H. Macromolecules 1995, 28, 6311-6316.
6. (a) Holder, S.; Blechert, S. Synlett 1996, June, 505-506.
7. (b) Crimmins, M. T.; King, B. W. J. Org Chem. 1996, 61, 4192-4193.
8. (c) Garro-Helion, F.; Guibe, F. Chem. Commun. 1996, 641-642.
9. (d) Fu, G. C.; Nguyen, S. T.; Grubbs, R. H. J. Am. Chem. Soc. 1993, 115, 9856-9857.
10. (a) Furstner, A.; Langemann, K. J. Org. Chem. 1996, 61, 3942-3943.
11. (b) Miller, S. J.; Grubbs, R. H. J. Am. Chem. Soc. 1995, 117, 5855-5856.
12. (c) Borer, B.; Deerenberg, S.; Bieraugel, H.; Pandit, U. K. Tetrahedron Lett. 1994, 35, 3191-3194.
13. Miller, S. J.; Kim, S.-H.; Chen, Z.-R.; Grubbs, R. H. J. Am. Chem. Soc. 1995, 117, 2108-2109.
14. Kim, S.-H.; Bowden, N.; Grubbs, R. H. J. Am. Chem. Soc. 1994, 116, 10801-10802.
15. For a recent review of olefin metathesis catalysts in organic synthesis, see Grubbs, R. H.; Miller, S. J.; Fu, G. C. Acc. Chem. Res. 1995, 28, 446-452.
16. Bowden, N.; Grubbs, R. H. Unpublished results.
17. 2 in this ring-closing metathesis reaction.
18. For background reading on the steric and electronic properties of phosphines, see: (a) Brown, T. L.; Lee, K. J. Coord. Chem. Rev. 1993, 128, 89-116. (b) Wilson, M. R.; Woska, D. C.; Prock, A.; Giering, W. P. Organometallics 1993, 12, 1742-1752. (c) Tolman, C. A. Chem. Rev. 1977, 77, 313-348.
19. For background reading on the steric and electronic properties of phosphines, see: (a) Brown, T. L.; Lee, K. J. Coord. Chem. Rev. 1993, 128, 89-116. (b) Wilson, M. R.; Woska, D. C.; Prock, A.; Giering, W. P. Organometallics 1993, 12, 1742-1752. (c) Tolman, C. A. Chem. Rev. 1977, 77, 313-348.
20. For background reading on the steric and electronic properties of phosphines, see: (a) Brown, T. L.; Lee, K. J. Coord. Chem. Rev. 1993, 128, 89-116. (b) Wilson, M. R.; Woska, D. C.; Prock, A.; Giering, W. P. Organometallics 1993, 12, 1742-1752. (c) Tolman, C. A. Chem. Rev. 1977, 77, 313-348.
21. 2). We found that the trifluoroacetate-containing catalyst polymerized norbornene at least ten times faster than the acetate-containing catalyst, and therefore we conclude that more electron withdrawing X groups produce more active catalysts.
22. Schwab, P.; Grubbs, R. H.; Ziller, J. W. J. Am. Chem. Soc. 1996, 118, 100-110.
23. It may be argued that breakdown of the metallacycle is the rate determining step, in which case our differential equations are only slightly altered, and still in agreement with our empirically derived rate expression. However, we believe that metallacycle formation is rate determining, as it corresponds to a formal two electron oxidation of the ruthenium center.
24. 1H NMR in the presence of excess phosphine.
25. The possiblity that the diene chelates the metal center to form a 16-electron complex cannot be ruled out, although entropically this seems unlikely without any predisposition of the diene toward chelation as in the case of butadiene, norbornadiene, or 1,5-cyclooctadiene.
26. 3, indicating relatively high barriers to both phosphine exchange and carbene rotation.
27. Moers, F. G.; Langhout, J. P. J. Inorg. Nucl. Chem. 1977, 39, 591-593.
28. Brown, L. D.; Barnard, C. F. J.; Daniels, J. A.; Mawby, R. J.; Ibers, J. A. Inorg. Chem. 1978, 17, 2932-2935.
29. For a brief discussion of the principle of microscopic reversibility, see for example: Laidler, K. J. Chemical Kinetics, 2nd ed.; McGraw-Hill: New York, 1965; pp 110-112.
30. For a brief discussion of the ligand trans influences and the kinetic trans effect, see for example: Collman, J. P.; Hegedus, L. S.; Norton, J. R.; Finke, R. G. Principles and Applications of Organotransition Metal Chemistry; University Science: Mill Valley, 1987; pp 241-244 and references therein.
31. Garlatti, R. D.; Tauzher, G. Inorg. Chim. Acta 1988, 142, 263-267.
32. (a) Seibles, L.; Deutsch, E. Inorg. Chem. 1977, 16, 2273-2278.
33. (b) Trogler, W. C.; Stewart, R. C.; Marzilli, L. G. J. Am. Chem. Soc. 1974, 96, 3697-3699.
34. (c) Tauzher, G.; Dreos, R.; Costa, G.; Green, M. J. Chem. Soc., Chem. Commun. 1973, 413-414.
35. (d) Crumbliss, A. L.; Wilmarth, W. K. J. Am. Chem. Soc. 1970, 92, 2593-2594.
36. For a discussion of molybdenum and tungsten catalyst activities, see: Progress in Inorganic Chemistry; Lippard, S. J., Ed.; Wiley: New York, 1991; Vol. 39, and references therein.
37. Comprehensive Coordination Chemistry; Wilkinson, G., Ed.; Pergamon: New York, 1987; Vol. 5.
38. It is likely that there is some degree of halogen exchange when catalysts containing Br or I are used. However, complexation of free phosphine is undoubtedly the predominant effect, since Cl-containing compounds such as 2c are activated by addition of CuCl to the extent that the ring-closing reaction is too fast to study under the standard reaction conditions.