A recyclable Ru-based metathesis catalyst

Journal of the American Chemical Society

Volumn 121, Issue 4, 1999, Pages 791-799

  Kingsbury, Jason S ^a   Harrity, Joseph P A ^a,b   Bonitatebus Jr , Peter J ^a   Hoveyda, Amir H ^a  

^a BOSTON COLLEGE   (United States)

^b UNIVERSITY OF SHEFFIELD   (United Kingdom)

Author keywords

[No Author keywords available]

Indexed keywords

CHELATE; METAL; OXYGEN; RUTHENIUM;

ARTICLE; CATALYST; METAL BINDING; MOLECULAR STABILITY; NUCLEAR MAGNETIC RESONANCE; SYNTHESIS; X RAY DIFFRACTION;

EID: 0033518572     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja983222u     Document Type: Article

References (42)

1. For recent reviews on olefin metathesis, see: (a) Schuster, M.; Blechert, S. Angew. Chem., Int. Ed. Engl. 1997, 109, 2036-2056. (b) Furstner, A. Top. in Catal. 1997, 4, 285-299. (c) Armstrong, S. K. J. Chem. Soc., Perkin Trans. 1 1998, 371-388. (d) Grabbs, R. H.; Chang, S. Tetrahedron 1998, 54, 4413-4450.
2. For recent reviews on olefin metathesis, see: (a) Schuster, M.; Blechert, S. Angew. Chem., Int. Ed. Engl. 1997, 109, 2036-2056. (b) Furstner, A. Top. in Catal. 1997, 4, 285-299. (c) Armstrong, S. K. J. Chem. Soc., Perkin Trans. 1 1998, 371-388. (d) Grabbs, R. H.; Chang, S. Tetrahedron 1998, 54, 4413-4450.
3. For recent reviews on olefin metathesis, see: (a) Schuster, M.; Blechert, S. Angew. Chem., Int. Ed. Engl. 1997, 109, 2036-2056. (b) Furstner, A. Top. in Catal. 1997, 4, 285-299. (c) Armstrong, S. K. J. Chem. Soc., Perkin Trans. 1 1998, 371-388. (d) Grabbs, R. H.; Chang, S. Tetrahedron 1998, 54, 4413-4450.
4. For recent reviews on olefin metathesis, see: (a) Schuster, M.; Blechert, S. Angew. Chem., Int. Ed. Engl. 1997, 109, 2036-2056. (b) Furstner, A. Top. in Catal. 1997, 4, 285-299. (c) Armstrong, S. K. J. Chem. Soc., Perkin Trans. 1 1998, 371-388. (d) Grabbs, R. H.; Chang, S. Tetrahedron 1998, 54, 4413-4450.
5. Harrity, J. P. A.; Visser, M. S.; Gleason, J. D.; Hoveyda, A. H. J. Am. Chem. Soc. 1997, 119, 1488-1489.
6. Harrity, J. P. A.; La, D. S.; Cefalo, D. R.; Visser, M. S.; Hoveyda, A. H. J. Am. Chem. Soc. 1998, 120, 2343-2351.
7. (a) Schwab, P.; France, M. B.; Ziller, J. W.; Grubbs, R. H. Angew. Chem., Int. Ed. Engl. 1995, 34, 2039-2041.
8. (b) Schwab, P.; Grubbs, R. H.; Ziller, J. W. J. Am. Chem. Soc. 1996, 118, 100-110.
9. (a) Schrock, R. R.; Murdzek, J. S.; Bazan, G. C.; Robbins, J.; DiMare, M.; O'Regan, M. J. Am. Chem. Soc. 1990, 112, 3875-3886.
10. (b) Bazan, G. C.; Schrock, R. R.; Cho, H.-N.; Gibson, V. C. Macromolecules 1991, 24, 4495-4502.
11. Johannes, C. W.; Visser, M. S.; Weatherhead, G. S.; Hoveyda, A. H. J. Am. Chem. Soc. 1998, 120, 8340-8347.
12. α dihedral angle; see: (a) Nguyen, S. T.; Grubbs, R. H.; Ziller, J. W. J. Am. Chem. Soc. 1993, 115, 9858-9859. (b) Dias, E. L.; Nguyen, S. T.; Grubbs, R. H. J. Am. Chem. Soc. 1997, 119, 3887-3897. In general, the magnitude of coupling between phosphine ligands and the α-proton of a carbene unit depends on their relative spatial orientation or geometry; see: (c) Klein, D. P.; Bergman, R. G. J. Am. Chem. Soc. 1989, 111, 3079-3080.
13. α dihedral angle; see: (a) Nguyen, S. T.; Grubbs, R. H.; Ziller, J. W. J. Am. Chem. Soc. 1993, 115, 9858-9859. (b) Dias, E. L.; Nguyen, S. T.; Grubbs, R. H. J. Am. Chem. Soc. 1997, 119, 3887-3897. In general, the magnitude of coupling between phosphine ligands and the α-proton of a carbene unit depends on their relative spatial orientation or geometry; see: (c) Klein, D. P.; Bergman, R. G. J. Am. Chem. Soc. 1989, 111, 3079-3080.
14. α dihedral angle; see: (a) Nguyen, S. T.; Grubbs, R. H.; Ziller, J. W. J. Am. Chem. Soc. 1993, 115, 9858-9859. (b) Dias, E. L.; Nguyen, S. T.; Grubbs, R. H. J. Am. Chem. Soc. 1997, 119, 3887-3897. In general, the magnitude of coupling between phosphine ligands and the α-proton of a carbene unit depends on their relative spatial orientation or geometry; see: (c) Klein, D. P.; Bergman, R. G. J. Am. Chem. Soc. 1989, 111, 3079-3080.
15. Recent mechanistic work by Grubbs indicates that this dynamic process is not energetically prohibitive. Carbene rotation is apparently the direct result of subtle variations made in the steric and/or electronic environments of a given Ru complex, implying that linear combinations of the two available π-bonding orbitals on Ru exist such that the metal-C double bond is not broken during the rotation process. For further discussion, see ref 7b.
16. 3 for Z = 4; T = 183(2) K. In the solid state, the structure contained a disordered pentane unit that was modeled over two positions with 60:40 occupancy. Further details, including tables of crystallographic data, are available in the Supporting Information.
17. For Ru-O chelate complexes with similar bond lengths, see: (a) Yang, H.; Alvarez-Gressier, M.; Lugan, N.; Mathieu, R. Organometallics 1997, 16, 1401-1409. (b) Lindner, E.; Mockel, A.; Mayer, H. A.; Fawzi, R. Chem. Ber. 1992, 125, 1363-1367. (c) Lindner, E.; Schober, U.; Fawzi, R.; Killer, W.; Englert, U.; Wegner, P. Chem. Ber. 1987, 120, 1621-1628. (d) Jeffrey, J. C.; Rauchfuss, T. B. Inorg. Chem. 1979, 18, 2658-2666. For examples of stronger Ru-O chelation and the corresponding bond lengths, see: (e) Lindner, E.; Mockel, A.; Mayer, H. A.; Kuhbauch, H.; Fawzi, R.; Steimann, M. Inorg. Chem. 1993, 32, 1266-1271. For related alkylidene metal-oxygen chelate complexes of chromium, see: (f) Dotz, K. H.; Popall, M.; Muller, G. J. Organomet. Chem. 1987, 334, 57-75.
18. For Ru-O chelate complexes with similar bond lengths, see: (a) Yang, H.; Alvarez-Gressier, M.; Lugan, N.; Mathieu, R. Organometallics 1997, 16, 1401-1409. (b) Lindner, E.; Mockel, A.; Mayer, H. A.; Fawzi, R. Chem. Ber. 1992, 125, 1363-1367. (c) Lindner, E.; Schober, U.; Fawzi, R.; Killer, W.; Englert, U.; Wegner, P. Chem. Ber. 1987, 120, 1621-1628. (d) Jeffrey, J. C.; Rauchfuss, T. B. Inorg. Chem. 1979, 18, 2658-2666. For examples of stronger Ru-O chelation and the corresponding bond lengths, see: (e) Lindner, E.; Mockel, A.; Mayer, H. A.; Kuhbauch, H.; Fawzi, R.; Steimann, M. Inorg. Chem. 1993, 32, 1266-1271. For related alkylidene metal-oxygen chelate complexes of chromium, see: (f) Dotz, K. H.; Popall, M.; Muller, G. J. Organomet. Chem. 1987, 334, 57-75.
19. For Ru-O chelate complexes with similar bond lengths, see: (a) Yang, H.; Alvarez-Gressier, M.; Lugan, N.; Mathieu, R. Organometallics 1997, 16, 1401-1409. (b) Lindner, E.; Mockel, A.; Mayer, H. A.; Fawzi, R. Chem. Ber. 1992, 125, 1363-1367. (c) Lindner, E.; Schober, U.; Fawzi, R.; Killer, W.; Englert, U.; Wegner, P. Chem. Ber. 1987, 120, 1621-1628. (d) Jeffrey, J. C.; Rauchfuss, T. B. Inorg. Chem. 1979, 18, 2658-2666. For examples of stronger Ru-O chelation and the corresponding bond lengths, see: (e) Lindner, E.; Mockel, A.; Mayer, H. A.; Kuhbauch, H.; Fawzi, R.; Steimann, M. Inorg. Chem. 1993, 32, 1266-1271. For related alkylidene metal-oxygen chelate complexes of chromium, see: (f) Dotz, K. H.; Popall, M.; Muller, G. J. Organomet. Chem. 1987, 334, 57-75.
20. For Ru-O chelate complexes with similar bond lengths, see: (a) Yang, H.; Alvarez-Gressier, M.; Lugan, N.; Mathieu, R. Organometallics 1997, 16, 1401-1409. (b) Lindner, E.; Mockel, A.; Mayer, H. A.; Fawzi, R. Chem. Ber. 1992, 125, 1363-1367. (c) Lindner, E.; Schober, U.; Fawzi, R.; Killer, W.; Englert, U.; Wegner, P. Chem. Ber. 1987, 120, 1621-1628. (d) Jeffrey, J. C.; Rauchfuss, T. B. Inorg. Chem. 1979, 18, 2658-2666. For examples of stronger Ru-O chelation and the corresponding bond lengths, see: (e) Lindner, E.; Mockel, A.; Mayer, H. A.; Kuhbauch, H.; Fawzi, R.; Steimann, M. Inorg. Chem. 1993, 32, 1266-1271. For related alkylidene metal-oxygen chelate complexes of chromium, see: (f) Dotz, K. H.; Popall, M.; Muller, G. J. Organomet. Chem. 1987, 334, 57-75.
21. For Ru-O chelate complexes with similar bond lengths, see: (a) Yang, H.; Alvarez-Gressier, M.; Lugan, N.; Mathieu, R. Organometallics 1997, 16, 1401-1409. (b) Lindner, E.; Mockel, A.; Mayer, H. A.; Fawzi, R. Chem. Ber. 1992, 125, 1363-1367. (c) Lindner, E.; Schober, U.; Fawzi, R.; Killer, W.; Englert, U.; Wegner, P. Chem. Ber. 1987, 120, 1621-1628. (d) Jeffrey, J. C.; Rauchfuss, T. B. Inorg. Chem. 1979, 18, 2658-2666. For examples of stronger Ru-O chelation and the corresponding bond lengths, see: (e) Lindner, E.; Mockel, A.; Mayer, H. A.; Kuhbauch, H.; Fawzi, R.; Steimann, M. Inorg. Chem. 1993, 32, 1266-1271. For related alkylidene metal-oxygen chelate complexes of chromium, see: (f) Dotz, K. H.; Popall, M.; Muller, G. J. Organomet. Chem. 1987, 334, 57-75.
22. For Ru-O chelate complexes with similar bond lengths, see: (a) Yang, H.; Alvarez-Gressier, M.; Lugan, N.; Mathieu, R. Organometallics 1997, 16, 1401-1409. (b) Lindner, E.; Mockel, A.; Mayer, H. A.; Fawzi, R. Chem. Ber. 1992, 125, 1363-1367. (c) Lindner, E.; Schober, U.; Fawzi, R.; Killer, W.; Englert, U.; Wegner, P. Chem. Ber. 1987, 120, 1621-1628. (d) Jeffrey, J. C.; Rauchfuss, T. B. Inorg. Chem. 1979, 18, 2658-2666. For examples of stronger Ru-O chelation and the corresponding bond lengths, see: (e) Lindner, E.; Mockel, A.; Mayer, H. A.; Kuhbauch, H.; Fawzi, R.; Steimann, M. Inorg. Chem. 1993, 32, 1266-1271. For related alkylidene metal-oxygen chelate complexes of chromium, see: (f) Dotz, K. H.; Popall, M.; Muller, G. J. Organomet. Chem. 1987, 334, 57-75.
23. 2Ru=CHPh (1) is commercially available from Strem Chemicals, Inc., at $60/g.
24. 2 in MeOH, followed by brief exposure to 1,1,3,3-tetramethylguanidine in the same vessel affords the diazo starting material (see the Experimental Section for details). For the use of tetramethylguanidine in the synthesis of o-substituted aryldiazoalkanes, see: Shankar, B. K. R.; Shechter, H. Tetrahedron Lett. 1982, 23, 2277-2280.
25. Stephenson, T. A.; Wilkinson, G. J. Inorg. Nucl. Chem. 1966, 28, 945-956.
26. CuCl is known to react with phosphines to make a marginally soluble, ill-defined complex; see: (a) Reference 7b. (b) Dias, E. L.; Grubbs, R. H. Organometallics 1998, 17, 2758-2767. (c) Comprehensive Coordination Chemistry; Wilkinson, G., Ed.; Permagon Press: New York, 1987; Vol. 5.
27. CuCl is known to react with phosphines to make a marginally soluble, ill-defined complex; see: (a) Reference 7b. (b) Dias, E. L.; Grubbs, R. H. Organometallics 1998, 17, 2758-2767. (c) Comprehensive Coordination Chemistry; Wilkinson, G., Ed.; Permagon Press: New York, 1987; Vol. 5.
28. CuCl is known to react with phosphines to make a marginally soluble, ill-defined complex; see: (a) Reference 7b. (b) Dias, E. L.; Grubbs, R. H. Organometallics 1998, 17, 2758-2767. (c) Comprehensive Coordination Chemistry; Wilkinson, G., Ed.; Permagon Press: New York, 1987; Vol. 5.
29. 2 solution at 22°C. For experimental details and additional crystallographic data, see the Supporting Information.
30. Nguyen, S. T.; Johnson, L. K.; Grubbs, R. H. J. Am. Chem. Soc. 1992, 114, 3974-3975.
31. Wu, Z.; Nguyen, S. T.; Grubbs, R. H.; Ziller, J. W. J. Am. Chem. Soc. 1995, 117, 5503-5511.
32. Variations in temperature and reaction time for the phosphine exchange afforded the same result. Because the reaction is nearly instantaneous, it is difficult to assess the identity of the kinetic product.
33. The catalytic metathesis activity of 11 and 13 toward highly strained cyclic olefins such as norbornene, bicyclo[3.2.0]hept-6-ene, and transcyclooctene was not probed. For the metathesis activity of related triphenylphosphine-substituted Ru systems toward these substrates, see: (a) Reference 16. (b) Wu, Z.; Benedicto, A. D.; Grubbs, R. H. Macromolecules 1993, 26, 4975-4977.
34. The catalytic metathesis activity of 11 and 13 toward highly strained cyclic olefins such as norbornene, bicyclo[3.2.0]hept-6-ene, and transcyclooctene was not probed. For the metathesis activity of related triphenylphosphine-substituted Ru systems toward these substrates, see: (a) Reference 16. (b) Wu, Z.; Benedicto, A. D.; Grubbs, R. H. Macromolecules 1993, 26, 4975-4977.
35. 1H NMR.
36. 2OPRu residue: C, 55.99; H, 7.55. Found: C, 56.36; H, 7.72).
37. 2 and the insensitivity of the catalyst to oxygen, moisture, and adventitious impurities during its reactions, see: Fu, G. C.; Nguyen, S. T.; Grubbs, R. H. J. Am. Chem. Soc. 1993, 115, 9856-9857.
38. Tallarico, J. A.; Bonitatebus, P. J., Jr.; Snapper, M. L. J. Am. Chem. Soc. 1997, 119, 7157-7158.
39. For catalyst 8, the propagating carbene proton signal is never detectable by NMR under the given reaction conditions. It is plausible that the highly active monophosphine propagating species is short-lived on the NMR time scale. The consumption of 8 was thus monitored relative to ferrocene as an internal standard (see Experimental Section for further details). Furthermore, a plot of -1n [8] vs time generated a curve with exponential and not linear character, suggesting that the kinetics are not first order in Ru. These numbers only represent an approximation of the relative activity profiles for 1 and 8.
40. Other recyclable metathesis catalyst systems have been recently reported. In a recent study, Grubbs and Nguyen prepared a series of polystyrene-divinylbenzene (PS-DVB)-supported Ru-vinylcarbene complexes and their metathesis activities were explored. Unfortunately, recovery and reuse of the catalysts led to small losses in activity (20% after each cycle), suggesting that the complexes experience a finite lifetime when bound to the polymer support. Moreover, reaction rates with the polymer-supported carbenes were orders of magnitude lower than that of their homogeneous analogues. See: Nguyen, S. T.; Grubbs, R. H. J. Organomet. Chem. 1995, 497, 195-200.
41. For recent studies on asymmetric ring-closing metathesis (ARCM), see: (a) Alexander, J. B.; La, D. S.; Cefalo, D. R.; Hoveyda, A. H.; Schrock, R. R. J. Am. Chem. Soc. 1998, 120, 4041-4042 and references therein. (b) La, D. S.; Alexander, J. B.; Cefalo, D. R.; Graf, D. D.; Hoveyda, A. H.; Schrock, R. R. J. Am. Chem. Soc. 1998, 120, 9720-9721.
42. For recent studies on asymmetric ring-closing metathesis (ARCM), see: (a) Alexander, J. B.; La, D. S.; Cefalo, D. R.; Hoveyda, A. H.; Schrock, R. R. J. Am. Chem. Soc. 1998, 120, 4041-4042 and references therein. (b) La, D. S.; Alexander, J. B.; Cefalo, D. R.; Graf, D. D.; Hoveyda, A. H.; Schrock, R. R. J. Am. Chem. Soc. 1998, 120, 9720-9721.