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

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." Naota, T.; Takaya, H.; Murahashi, S.-I. Chem. Rev. 1998, 98, Electron configuration: (Kr)4d 7 5s 1 Oxidation states: 2,3,4,6,8

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

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

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 o C). 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 C5H4RC5H4R Okuda, J. Top. Curr. Chem. 1992, 160, 97. Halterman, R. L. Chem. Rev. 1992, 92, 965.

11 C 5 HMe 4 R R=Me, Et, nPr, nBu and Ph J. Organomet. Chem. 1977, 136, 1. Org. Synth. 1987, 65, 42. R=iPr J. Organomet. Chem. 1998, 559, 181. R=CF 3 J. Am. Chem. Soc. 1992, 114, R: containing terminal functional groups Synthesis 1993, 684.

12 C 5 HMe 4 R R=Me J. Organomet. Chem. 1983, 243, 119. Organometallics 1988, 7, Inorg. Synth. 1992, 29, R=CH 2 CH 2 CH=CH 2 J. Organomet. Chem. 1988, 344, C1-C4. R=tBu J. Organomet. Chem. 1996, 520, 265.

13 C 5 H 2 R 1 R 2 R 3 CO 2 Et Hatanaka, M; Himeda, Y.; Ueda, I. J. Chem. Soc., Chem. Commun. 1990, 526.

14 C 5 HR 4 R’ Xi, Z.; Li, P. Angew. Chem., Int. Ed. Engl. 2000, 39, R: Me, Et, n-Pr, n-Bu, Ph··· R’CHO: aliphatic or aromatic aldehyde

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(η 5 -C 5 R 5 )(MeCN) 3 ] + Complexes Fagan, P. J.; Ward, M. D.; Calabrese, J. C. J. Am. Chem. Soc. 1989, 111, 1698 Steinmetz, B.; Schenk, W. A. Organometallics 1999, 18, 943 Mbaye, M. D.; Demerseman, B.; Renaud, J.-L.; Toupet, L.; Bruneau, C. Adv. Synth. Catal. 2004, 346 (7), 835

18 [Ru( η 5 -C 5 R 5 )(MeCN) 3 ] + Complexes T. P. Gill, K. R. Mann, Organometallics 1982, 1, 485. Komatsuzaki, N.; Uno, M.; Kikuchi, H.; Takahashi, S. Chem. Lett. 1996, 677.

19 Ru( η 5 -C 5 R 5 )( η 4 -diene)Cl complexes Alvarez, P.; Gimeno, J.; Lastra, E.; Garcia-Granda, S.; Van der Maelen, J. F.; Bassetti, M. Organometallics 2001, 20, 3762 Albers, M. O.; Robinson, D. J.; Shaver, A.; Singleton, E. Organometallics 1986, 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, Trost, B. M.; Pinkerton, A. B.; Kremzow, D. J. Am. Chem. Soc. 2000, 122,

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, 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,

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, 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, 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,

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,

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

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,

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 New sterically demanding catalysts with bulky, electron rich C 5 R 5 ligands New optically active catalysts with chiral C 5 R 4 R* ligands Polymerizable catalysts for the recovery and recycling of catalysts. “Teaching An Old Dog New Tricks”

43 Acknowledgement Laboratoire de Catalyse et Organométalliques 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:

44 Thank you for your attention!

45 Proposed Mechanism

46 Ruthenium Hydride