Inter- and intramolecular thermal activation of aliphatic C-H bonds mediated by complexes containing the fragments [{Cy2P(CH2)nPCy2}M] (n = 1-4, M = Rh, Ru)

Chemische Berichte

Volumn 130, Issue 5, 1997, Pages 555-558

  Leitner, Walter ^a   Six, Christian ^a  

^a MAX PLANCK INSTITUT FÜR KOHLENFORSCHUNG   (Germany)

Author keywords

C H activation; Dehydrogenation; Homogeneous catalysis; Phosphane complexes

Indexed keywords

EID: 0004131480     PISSN: 00092940     EISSN: None     Source Type: Journal    
DOI: 10.1002/cber.19971300504     Document Type: Article

References (47)

1. [1a] Selective Hydrocarbon Activation (Eds.: J. A. Davies, P. C. Watson, J. F. Liebman, A. Greenberg), VCH, Weinheim, 1990;
2. [1b] R. H. Crabtree, in The Chemistry of Functional Groups (Eds.: S. Patai, Z. Rappoport), Wiley, Chichester, 1992, 653-679.
3. [2a] A. D. Ryabov, Chem. Rev. 1990, 90, 403;
4. B. A. Arndtsen, R. G. Bergman, T. A. Mobley, T. H. Peterson, Acc. Chem. Res. 1995, 28, 154;
5. [2c] R. H. Crabtree, Chem. Rev. 1995, 95, 987.
6. [3a) B. A. Arndtsen, R. G. Bergman, Science 1995,270, 1970;
7. [3b] J. C. W. Lohrenz, H. Jacobsen, Angew. Cltem. 1996, 108, 1403;
8. Angew. Chent. Int. Ed. Engl. 1996, 35, 1305 and references therein.
9. [4a] D. Baudry, M. Ephritikhine, H. Felkin, R. Holmes-Smith, J. Chem. Soc. Chem. Commun. 1983, 788;
10. [4b] H. Felkin, T. Fillebeen-Khan, Y. Gault, R. Holmes-Smith, J. Zakrzewski, Tetrahedron Lett. 1984, 25, 1279;
11. [4c] H. Felkin, T. FillebeenKhan, R. Holmes-Smith, L. Yingrui, ibid. 1985, 26, 1999.
12. [5a] M. J. Burk, R. H. Crabtree, C. P. Parnell, R. J. Urlate, Organometallics 1984, 3, 816;
13. [5b] M. J. Burk, R. H. Crabtree, D. V. McGrath, J. Chem. Soc. Chem. Commun. 1985, 1829;
14. [5c] M. J. Burk, R. H. Crabtree, J. Am. Chem. Soc. 1987, 109, 8025;
15. [5d] T. Aoki, R. H. Crabtree, Organometallics 1993, 12, 294.
16. [6a] T. Fuji, Y. Saito, J. Chem. Soc. Chem. Commun. 1990, 757;
17. [6b] T. Fuji, Y. Higashino, Y. Saito, J. Chem. Soc. Daltan Trans. 1993, 517.
18. [7a] J. A. Macuire, A. S. Goldman, J. Am. Chem. Soc. 1991, 113, 6706;
19. [7b] J. A. Maguire, A. Petrillo, A. S. Goldman, ibid. 1992, 114, 9492;
20. [7c] K. Wang, M. E. Goldman, T. J. Emge, A. S. Goldman, J. Organomet. Chem. 1996, 518, 55.
21. [8a] Belli, C. M. Jensen, Organometallics 1996, 75, 1532; Efficient transfer-dehydrogenation of cyclooctane by using Ir and Rh complexes containing a terdentate "pincer" ligand with two Rh donor groups in trans position
22. [8b] and chelating P∩O lieands
23. [8c] have been reported while this work was in progress:
24. [8b] M. Gupta, C. Hagen, R. J. Flesher, W. C. Kaska, C. M. Jensen, J. Chem. Soc. Chem. Commun. 1996, 2083;
25. [8c] P. Braunstein, Y. Chauvin, J. Nähring, A. DeCian, J. Fischer, A. Tiripicchio, F. Ugozzoli, Organometallics 1996, 15, 5551.
26. [9a] Y. Fujiwara, K. Takaki, Y. Taniguchi, Synlett 1996, 691;
27. [9b] M. Lin, T. E. Hogan, A. Sen, J. Am. Chem. Soc. 1996, 118, 4574.
28. [10a] Comprehensive Organometallic Chemistry II, Vol. 12 (Eds.: E. W. Abel, F. G. A. Stone, G. Wilkinson), Pergamon, Oxford, 1995.
29. [10b] R. H. Crabtree, The Organometallic Chemistry of the Transition Metals, 2nd ed., Wiley, New York, 1994.
30. [11a] R. Fornika, H. Görls, B. Seemann, W. Leitner, J. Chem. Soc. Chem. Commun. 1995, 1479.
31. [11b] K. Angermund, W. Baumann, E. Dinjus, R. Fornika, H. Görls, M. Kessler, C. Krüger, W. Leitner, F. Lutz, Chem. Eur. J., in press.
32. P. Hofmann, C. Meier, W. Hiller, M. Heckel, J. Riede, M. U. Schmidt, J. Organomet. Chem. 1995, 490, 51.
33. For use of related complexes in homogeneous catalysis see:
34. [13a] J. P. Genêt, V. Ratovelomanana-Vida!, M. C. Cano de Andrade, X. Pfister, P. Guerreiro, J. Y. Lenoir, Tetrahedron Letters 1995, 36, 4801.
35. [13b] H. Doucet, B. Martin-Vaca, C. Bruneau, P. H. Dixneuf, J. Org. Chem. 1995, 60, 7247.
36. [13c] J. M. Brown, M. Rose, F. I. Knight, A. Wienand, Recl. Trav. Chim. Pays-Bas 1995, 114, 242.
37. 2] has been investigated independently by Jolly and co-workers: P. W. Jolly, S. Holle, submitted for publication.
38. 3-allyl ligands.
39. We found similar concentrations of 4 after 48 h at 170°C in a control experiment using a commercial Ru/C catalyst (5% Ru).
40. D. R. Anton, R. H. Crabtree, Organometallics 1983, 2, 855.
41. A detailed description of the NMR spectroscopic characterization of complex 5 on basis of homo- and heteronuclear ID- and 2D-NMR decoupling experiments will be reported separately: B. Gabor, H. Görls, W. Leitner, R. Mynott, P. Philipps, C. Six, to be published.
42. 3P ligand at Ruthenium most recently:
43. [18a] M. L. Christ, S. Sabo-Etienne, B. Chaudret, Organometallics 1995, 14, 1082.
44. [18b] A. Borowski, S. Sabo-Etienne, M. L. Christ, B. Donnadieu, B. Chaudret, Organometallics 1996, 15, 1427.
45. [18c] For dehydrogenation to yield cyclohexene see: S. Hietkamp, D. J. Hufkens, K. Vrieze, J. Organomet. Chem. 1978, 152, 347.
46. [19a] R. Fornika, E. Dinjus, H. Görls, W. Leitner, J. Organomet. Chem. 1996, 511, 145.
47. [19b] F. Gassner, E. Dinjus, H. Görls, W. Leitner, Organometallics 1996, 75, 2078 and references therein.