Rapid catalytic oxygenation of hydrocarbons by ruthenium pentafluorophenylporphyrin complexes: Evidence for the involvement of a Ru(III) intermediate

Journal of the American Chemical Society

Volumn 118, Issue 37, 1996, Pages 8961-8962

  Groves, John T ^a   Bonchio, Marcella ^a,b   Carofiglio, Tommaso ^a,b   Shalyaev, Kirill ^a  

^a PRINCETON UNIVERSITY   (United States)

^b UNIVERSITY OF PADOVA   (Italy)

Author keywords

[No Author keywords available]

Indexed keywords

ARTICLE; CATALYSIS; DRUG SYNTHESIS; HYDROXYLATION; REACTION ANALYSIS; ULTRAVIOLET SPECTROPHOTOMETRY;

EID: 0029811204     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja9542092     Document Type: Article

References (36)

1. (a) Groves, J. T.; Han, Y.-Z. In Cytochrome P-450. Structure, Mechanism and Biochemistry; Ortiz de Montellano, P. R., Ed.; Plenum Press: New York, 1995: pp 3-48.
2. (b) Groves, J. T.; Nemo, T. E. J. Am. Chem. Soc. 1983, 105, 6243-6248.
3. (c) Activation and functionalization of alkanes; Hill, C. L., Ed.; John Wiley & Sons: New York, 1989.
4. Selective Hydrocarbon Activation: Principle and Progress; Davies, J. A., et al., Eds; VCH: New York, 1994.
5. (a) Metalloporphyrins in Catalytic Oxidations; Sheldon, R. A., Ed.; M. Dekker: New York, 1994.
6. (b) Mlodnika, T.; James. B. R. In Metalloporphyrin Catalyzed Oxidations: Montanari, F., Casella, L., Eds.; Kluwer: Dordrecht, The Netherlands, 1994; p 121.
7. (a) Groves, J. T.; Quinn, R. Inorg. Chem. 1984, 23, 3844-3846.
8. (b) Groves, J. T.; Quinn, R, J. Am. Chem. Soc. 1985, 107, 5790-5792.
9. (c) Groves, J. T.; Ahn, K.-H. Inorg. Chem. 1987, 26, 3831-3833.
10. (d) Groves, J. T.; Quinn, R. U.S. Patent 4,822,899, April 18, 1989.
11. Groves, J. T.; Roman, J. S. J. Am. Chem. soc. 1995, 117, 5594-5595.
12. (a) Higuchi, T.; Satake, C.; Hirobe, M. J. Am. Chem. Soc. 1995, 117, 8879-8880.
13. (b) Ohtake, H.; Higuchi, T.; Hirobe, M. Heterocycles 1995 and references therein.
14. (c) Higuchi, T. J. Synth. Org. Chem. Jpn. 1995, 53, 644-644.
15. (a) Ellis, P. E.; Lyons, J. E. Coord, Chem. Rev. 1990, 105, 181-193.
16. (b) Birnbaum, E. R.; Schaefer, W. P.; Labinger, J. A.; Bercaw, J. E., Gray, H. B. Inorg. Chem. 1995, 34, 1751-1755.
17. (c) Murahashi, S.-I.; Naota, T.; Komiya, N. Tetrahedron Lett. 1995, 36, 8059-8062.
18. 3, nm) 404, 524. 554. Cf. ref Tc.
19. IV-oxo porphyrin based systems (cf. ref 4 and Ho, C.; Leung, W.-H.; Che, C.-M. J. Chem. Soc., Dalton Trans. 1991, 2933-2939.)
20. Degradation of the active catalyst at higher catalyst concentration, which is more pronounced with the less reactive substrates, would account for the high activity at lower catalyst concentration (Table 1, entry 2). Also the identity of the axial ligand X, in Scheme I, is probably concentration dependent, thus further affecting the reaction rates.
21. Unfiltered irradiation (tungsten lamp, 300 W) caused the rapid degradation of the porphyrin ligand.
22. (a) Dolphin, D.; James, B. R.; Leung, T. Inorg. Chim. Acta 1983, 79, 25-27.
23. (b) Leung, T.; James, B. R.; Dolphin, D. Inorg. Chim. Acta 1983, 79, 180-181.
24. (c) Barley, M.; Becker, J. Y.; Domazetis, G.; Dolphin, D.; James, B. R. Can. J. Chem. 1983, 61, 2389-2396.
25. (d) James, B. R.; Dolphin, D.: Leung, T. W.; Einstein, F. W.; Willis, A. C. Can. J. Chem. 1984, 62, 1238-1245.
26. (e) James, B. R.; Mikkelsen, S. R.; Leung, T. W.; Williams, G. M., Wong, R. Inorg. Chim. Acta B 1984, 85, 209-213.
27. (f) For a review, see: James, B. R. In Fundamentals of Research in Homogeneous Catalvsis; Shilov, A. E., Ed. Gordon Breach: New York, 1986; pp 309-324.
28. -1 (ν C=O).
29. 2NO was added to a solution of 3 at -50 °C. The substrate was added after 4a formed at 25 °C. The reaction mixture was then heated at 65 °C.
30. -1; (In k = -9.73, -10.76, -12.39 at 338, 328, and 318 K, respectively).
31. 2 at 65 °C. maximum rate = 36 turnovers/min (entry 6, Table 1).
32. Groves, J. T.; Ahn, K.-H.; Quinn, R. J. Am. Chem. Soc. 1988, 110, 4217-4220.
33. 2] in 48 h.
34. 2] in the presence of adamantane.
35. 2] was observed during catalysis.
36. 3, nm) 440, 524, 560.