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Cyclopentadienyl-Ruthenium Catalysts --- One Group of Ru(II) Complexes

Cyclopentadienyl-Ruthenium Catalysts --- One Group of Ru(II) Complexes. Huijun ZHANG 2007-07-13. Content. Introduction Cyclopentadienes Cyclopentadienyl-Ruthenium Their Applications Outlook. Content. Introduction Cyclopentadienes Cyclopentadienyl-Ruthenium Their Applications Outlook.

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Cyclopentadienyl-Ruthenium Catalysts --- One Group of Ru(II) Complexes

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  1. Cyclopentadienyl-Ruthenium Catalysts--- One Group of Ru(II) Complexes Huijun ZHANG 2007-07-13

  2. Content Introduction Cyclopentadienes Cyclopentadienyl-Ruthenium Their Applications Outlook

  3. Content Introduction Cyclopentadienes Cyclopentadienyl-Ruthenium Their Applications Outlook

  4. Ruthenium Complexes “Ruthenium complexes have a variety of useful characteristics including high electron transfer ability, high Lewis acidity, low redox potentials, and stabilities of reactive metallic species such as oxometals, metallacycles, and metal carbene complexes." Electron configuration: (Kr)4d75s1 Oxidation states: 2,3,4,6,8 Naota, T.; Takaya, H.; Murahashi, S.-I. Chem. Rev. 1998, 98, 2599.

  5. Ruthenium Complexes Naota, T.; Takaya, H.; Murahashi, S.-I. Chem. Rev. 1998, 98, 2599.

  6. Cyclopentadienyl-Ruthenium Complexes Ruthenium-Catalyzed Reactions —A Treasure Trove of Atom-Economic Transformations Trost, B. M.; Frederiksen, M. U.; Rudd, M. T. Angew. Chem., Int. Ed.Engl. 2005,44,6630

  7. Cyclopentadienyl-Ruthenium Complexes Cp- and Cp*-Ru(II) Complexes: Relationship between Structures and Reactivities: Dérien, S.; Dixneuf, P. H. J. Organomet. Chem.2004, 689, 1382 Bruneau, C.; Renaud, J-L.; Demerseman, B. Chem. Eur. J. 2006,12,5178

  8. Content Introduction Cyclopentadienes Cyclopentadienyl-Ruthenium Their Applications Outlook

  9. Key Features of Cp Ligands • The M-Cp bond dissociation is large (ferrocene is stable to 400 oC). • The ligand blocks several coordination sites. • The ligand tends not to get involved chemically (although it certainly can from time to time). • It has excellent NMR properties.

  10. C5H4R Okuda, J. Top. Curr. Chem. 1992, 160, 97. Halterman, R. L. Chem. Rev. 1992, 92, 965.

  11. C5HMe4R R=Me, Et, nPr, nBu and PhJ. Organomet. Chem.1977, 136, 1. Org. Synth.1987, 65, 42. R=iPr J. Organomet. Chem.1998, 559, 181. R=CF3J. Am. Chem. Soc.1992, 114, 6942. R: containing terminal functional groupsSynthesis1993, 684.

  12. C5HMe4R R=Me J. Organomet. Chem.1983, 243, 119. Organometallics1988, 7, 1828. Inorg. Synth.1992, 29, 193. . R=CH2CH2CH=CH2J. Organomet. Chem.1988, 344, C1-C4. R=tBu J. Organomet. Chem.1996, 520, 265.

  13. C5H2R1R2R3CO2Et Hatanaka, M; Himeda, Y.; Ueda, I. J. Chem. Soc., Chem. Commun.1990, 526.

  14. C5HR4R’ R: Me, Et, n-Pr, n-Bu, Ph··· R’CHO: aliphatic or aromatic aldehyde Xi, Z.; Li, P.Angew. Chem.,Int. Ed.Engl. 2000,39,2950.

  15. Recent Two Examples Funami, H.; Kusama, H.; Iwasawa, N. Angew. Chem. Int. Ed.2007, 46, 909. Lee, J. H.; Toste, F. D. Angew. Chem. Int. Ed. 2007, 46, 912.

  16. Content Introduction Cyclopentadienes Cyclopentadienyl-Ruthenium Their Applications Outlook

  17. [Ru(η5-C5R5)(MeCN)3]+ Complexes Fagan, P. J.; Ward, M. D.; Calabrese, J. C. J. Am. Chem. Soc.1989, 111, 1698 Steinmetz, B.; Schenk, W. A. Organometallics1999, 18, 943 Mbaye, M. D.; Demerseman, B.; Renaud, J.-L.; Toupet, L.; Bruneau, C. Adv. Synth. Catal.2004, 346 (7), 835

  18. [Ru(η5-C5R5)(MeCN)3]+ Complexes T. P. Gill, K. R. Mann, Organometallics1982, 1, 485. Komatsuzaki, N.; Uno, M.; Kikuchi, H.; Takahashi, S. Chem. Lett.1996, 677.

  19. Ru(η5-C5R5)(η4-diene)Cl complexes Alvarez, P.; Gimeno, J.; Lastra, E.; Garcia-Granda, S.; Van der Maelen, J. F.; Bassetti, M. Organometallics2001, 20, 3762 Albers, M. O.; Robinson, D. J.; Shaver, A.; Singleton, E. Organometallics1986, 5, 2199

  20. Content Introduction Cyclopentadienes Cyclopentadienyl-Ruthenium Their Applications Outlook

  21. Cp-Ru Catalyzed C-C Bond Formation Reactions • Reactions Involving Ruthenacyclopentanes, Ruthenacyclopentenes, Ruthenacyclopentadienes • Heteroatom Additions to Alkynes • Reactions Involving Additions of Diazo Compounds • Reactions Initiated by Hydrometalations • Regioselective Allylation of Nuclephiles • Reactions Initiated by C-H Bond Activation

  22. Reactions Involving Ruthenacyclopentanes Trost, B. M.; Pinkerton, A. B. J. Am. Chem. Soc. 1999, 121, 4068.

  23. Reactions Involving Ruthenacyclopentane Trost, B. M.; Pinkerton, A. B. J. Am. Chem. Soc. 1999, 121, 10842. Trost, B. M.; Pinkerton, A. B.; Kremzow, D. J. Am. Chem. Soc. 2000, 122, 12007.

  24. Reactions Involving Ruthenacyclopentane Fujiwhara, M.; Nishikawa, T.; Hori, Y. Org. Lett. 1999, 1, 1635.

  25. Reactions Involving Ruthenacyclopentene An Alder-Ene Type Reaction: Trost, B. M.; Indolese, A. J. Am. Chem. Soc. 1993, 115, 4361. Trost, B. M.; Indolese, A. F.; Mu¨ ller, T. J. J.; Treptow, B. J. Am. Chem. Soc. 1995, 117, 615.

  26. Reactions Involving Ruthenacyclopentene Trost, B. M.; Müller, T. J. J. J. Am. Chem. Soc. 1994, 116, 4985.

  27. Reactions Involving Ruthenacyclopentene Trost, B. M.; Martinez, J. A.; Kulaweic, R. J.; Indolese, A. F. J.Am. Chem. Soc. 1993, 115, 10402.

  28. Reactions Involving Ruthenacyclopentene De´rien, S.; Dixneuf, P. H. J. Chem. Soc. Chem. Commun. 1994, 2551.

  29. Reactions Involving Ruthenacyclopentene Matsushima, Y.; Kikuchi, H.; Uno, M.; Takahashi, S. Bull.Chem. Soc. Jpn. 1999, 72, 2475. Kikuchi, H.; Uno, M.;Takahashi, S. Chem. Lett. 1997, 1273.

  30. Reactions Involving Ruthenacyclopentadiene Yamamoto, Y.; Kitahara, H.; Ogawa, R.; Itoh, K J. Org. Chem. 1998, 63, 9610. Yamamato, Y.; Kitahara, H.; Ogawa, R.; Kawaguchi, H.; Tatsumi, K.; Itoh, K. J. Am. Chem. Soc. 2000, 122, 4310.

  31. Heteroatom Additions to Alkynes Additions of Water Trost, B. M.; Krause, L.; Portnoy, M. J. Am. Chem. Soc. 1997, 119, 11319.

  32. Heteroatom Additions to Alkynes Intramollecular Version Trost, B. M.; Brown, R. E.; Toste, F. D. J. Am. Chem. Soc. 2000,122, 5877.

  33. Heteroatom Additions to Alkynes Additions of Halides Trost, B. M.; Pinkerton, A. B. J. Am. Chem. Soc. 1999, 121, 1988.

  34. Heteroatom Additions to Alkynes Additions of Carboxylic Acids Le Paih, J.; Monnier, F.; Dérien, S. J. Am. Chem. Soc.,2003, 125, 11964.

  35. Reactions Involving Additions of Diazo Compounds Le Paih, J.; Dérien, S.; Özdemir, I.; Dixneuf, P. H. J. Am. Chem.Soc. 2000, 122, 7400.

  36. Reactions Initiated by Hydrometalations Le Paih, J.; Rodrı´guez, D. C.; De´rien, S.; Dixneuf, P. H. Synlett 2000, 95.

  37. Regioselective Allylation of Nuclephiles Kondo, T.; Ono, H.; Satake, N.; Mitsudo, T.; Watanabe, Y. Organometallics 1995, 14, 1945. Trost, B. M.; Fraisse, P. L.; Ball, Z. T.; Angew. Chem. Int. Ed. 2002, 41, 1059.

  38. Oxidative Addition of Allylic Substrate Key Step in Ruthenium-Catalysed Allylic Substitution Reactions Bruneau, C.; Renaud, J-L.; Demerseman, B. Chem. Eur. J. 2006,12,5178

  39. Planar Chiral Ruthenium Catalysts Matsushima, Y.; Onitsuka, K.; Kondo, T.; Mitsudo, T.; Takahashi, S. J. Am. Chem. Soc. 2001, 123, 10405.

  40. Reactions Initiated by C-H Bond Activation Trost, B. M.; Toste, F. D. J. Am. Chem. Soc. 1999, 121, 9728.

  41. Content Introduction Cyclopentadienes Cyclopentadienyl-Ruthenium Their Applications Outlook

  42. Outlook “Teaching An Old Dog New Tricks” • New sterically demanding catalysts with bulky, electron rich C5R5 ligands • New optically active catalysts with chiral C5R4R* ligands • Polymerizable catalysts for the recovery and recycling of catalysts.

  43. Acknowledgement Prof. Zhenfeng Xi, Prof. Zhiping Li Prof. Pierre Dixneuf, Dr. Christian Bruneau, Dr. Bernard Demerseman All Professors in the Institute of Organic Chemistry All my lab mates Peking U. Team: Rennes U. Team: Laboratoire de Catalyse et Organométalliques

  44. Thank you for your attention!

  45. Proposed Mechanism

  46. Ruthenium Hydride

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