Formation of iridabenzenes by coupling of iridacyclopentadienes and alkenes

Angewandte Chemie - International Edition

Volumn 45, Issue 3, 2006, Pages 474-477

  Álvarez, Eleuterio ^a   Paneque, Margarita ^a   Poveda, Manuel L ^a   Rendón, Nuria ^a  

^a INSTITUTO DE INVESTIGACIONES QUÍMICAS   (Spain)

Author keywords

Aromaticity; C C coupling; Iridium; Metallabenzenes; Metallacycles

Indexed keywords

AMINES; IRIDIUM; PROPYLENE; SYNTHESIS (CHEMICAL);

AROMATICCITY; C-C COUPLING; METALLABENZENES; METALLCYCLES;

BENZENE;

EID: 30444440283     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200502437     Document Type: Article

References (36)

1. a) J. R. Bleeke, Chem. Rev. 2001, 101, 1205;
2. b) D. L. Thorn, R. Hoffmann, Nouv. J. Chim. 1979, 3, 39;
3. for recent theoretical work on this type of compound, see: c) M. A. Iron, A. C. B. Lucassen, H. Cohen, M. E. van der Boom, J. M. L. Martin, J. Am. Chem. Soc. 2004, 126, 11699;
4. d) M. A. Iron, J. M. L. Martin, M. E. van der Boom, J. Am. Chem. Soc. 2003, 125, 13020.
5. C. S. Chin, H. Lee, Chem. Eur. J. 2004, 10, 4518.
6. For recent examples, see: a) H. Xia, G. He, H. Zhang, T. B. Wen, H. H. Y. Sung, I. D. Williams, G. Jia, J. Am. Chem. Soc. 2004, 126, 6862;
7. b) P. Barrio, M. A. Esteruelas, E. Oñate, J. Am. Chem. Soc. 2004, 126, 1946;
8. c) M. Paneque, C. M. Posadas, M. L. Poveda, N. Rendón, V. Salazar, E. Oñate, K. Mereiter, J. Am. Chem. Soc. 2003, 125, 9898;
9. d) V. Jacob, T. J. R. Weakley, M. M. Haley, Angew. Chem. 2002, 114, 3620;
10. Angew. Chem. Int. Ed. 2002, 41, 3470.
11. M. Paneque, M. L. Poveda, N. Rendón, K. Mereiter, J. Am. Chem. Soc. 2004, 126, 1610.
12. 4 insertion, as in 5 (unpublished results).
13. E. Alvarez, M. Gómez, M. Paneque, C. M. Posadas, M. L. Poveda, N. Rendón, L. L. Santos, S. Rojas-Lima, V. Salazar, K. Mereiter, C. Ruiz, J. Am. Chem. Soc. 2003, 125, 1478.
14. A hydride-olefin complex related to 3a was also formed in 10% yield under these conditions. This complex and 6 are formed through separate kinetic pathways: 6 is stable up to 100°C, whereas the hydride-olefin species is converted at 80°C into a hydride-allyl complex related to 4a. These two species were fully characterized as shown and will be reported in a forthcoming full paper. We anticipate that the Me group from the propene appears in both complexes at the α position of the olefinic or the allyl chain, respectively, indicating that the propene can insert into the Ir-C bond of 1 to give the two possible regioisomers. (Chemical Equation Presented)
15. [3c]
16. As suggested by a referee, intermediate B may be reached by a sequence of olefin insertion and H transposition through the metal center. However, in this case it is difficult to understand why the hydride intermediate involved does not transform into an allyl species as described in Scheme 1 and reference [7]. The same reasoning applies to intermediate D in Scheme 5.
17. a) L. Giannini, G. Guillemot, E. Solari, C. Floriani, N. Re, A. Chiesi-Villa, C. Rizzoli, J. Am. Chem. Soc. 1999, 121, 2797;
18. b) J. S. Freundlich, R. R. Schrock, W. M. Davis, J. Am. Chem. Soc. 1996, 118, 3643;
19. c) M. Paneque, M. L. Poveda, L. L. Santos, E. Carmona, A. Lledós, G. Ujaque, K. Mereiter, Angew. Chem. 2004, 116, 3794;
20. Angew. Chem. Int. Ed. 2004, 43, 3708;
21. d) G. Parkin, E. Bunel, B. J. Burger, M. S. Trimmer, A. van Asselt, J. E. Bercaw, J. Mol. Catal. 1987, 41, 29;
22. e) O. V. Ozerov, L. A. Watson, M. Pink, K. G. Caulton, J. Am. Chem. Soc. 2003, 125, 9604;
23. f) O. V. Ozerov, L. A. Watson, M. Pink, K. G. Caulton, J. Am. Chem. Soc. 2004, 126, 6363.
24. a) F. M. Alías, P. J. Daff, M. Paneque, M. L. Poveda, E. Carmona, P. J. Pérez, V. Salazar, Y. Alvarado, R. Atencio, R. Sánchez- Delgado, Chem. Eur. J. 2002, 8, 5132;
25. b) F. M. Alías, M. L. Poveda, M. Sellin, E. Carmona, J. Am. Chem. Soc. 1998, 120, 5816.
26. E. Carmona, M. Paneque, M. L. Poveda, Dalton Trans. 2003, 4022.
27. D. H. Lee, J. Chen, J. W. Faller, R. H. Crabtree, Chem. Commun. 2001, 213.
28. R. R. Schrock, S. W. Seidel, N. C. Mösch-Zanetti, K-Y. Shih, M. B. O'Donoghue, W. M. Reiff, J. Am. Chem. Soc. 1997, 119, 11876.
29. α-Alkyl or -aryl eliminations, with cleavage of a C-C bond, are rare; see, for example: a) K. Ferré, G. Poignant, L. Toupet, V. Guerchais, J. Organomet. Chem. 2001, 629, 19;
30. b) M. Albrecht, G. van Koten, Angew. Chem. 2001, 113, 3866;
31. Angew. Chem. Int. Ed. 2001, 40, 3750;
32. c) B. Rybtchinski, D. Milstein, Angew. Chem. 1999, 111, 918;
33. Angew. Chem. Int. Ed. 1999, 38, 870.
34. The stereochemistry of the H migration is based only in ample literature precedents of related systems.
35. Preliminary kinetic studies are in accord with this mechanism: R. P. Hughes, H. A. Trujillo, J. W. Egan, Jr., A. L. Rheingold, J. Am. Chem. Soc. 2000, 122, 2261.
36. This compound is also accessible from the reaction of 2 with acetonitrile.