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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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content
Content

Introduction

Cyclopentadienes

Cyclopentadienyl-Ruthenium

Their Applications

Outlook

content3
Content

Introduction

Cyclopentadienes

Cyclopentadienyl-Ruthenium

Their Applications

Outlook

ruthenium complexes
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.

ruthenium complexes5
Ruthenium Complexes

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

cyclopentadienyl ruthenium complexes
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

cyclopentadienyl ruthenium complexes7
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

content8
Content

Introduction

Cyclopentadienes

Cyclopentadienyl-Ruthenium

Their Applications

Outlook

key features of cp ligands
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.
c 5 h 4 r
C5H4R

Okuda, J. Top. Curr. Chem. 1992, 160, 97.

Halterman, R. L. Chem. Rev. 1992, 92, 965.

c 5 hme 4 r
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.

c 5 hme 4 r12
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.

c 5 h 2 r 1 r 2 r 3 co 2 et
C5H2R1R2R3CO2Et

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

c 5 hr 4 r
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.

recent two examples
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.

content16
Content

Introduction

Cyclopentadienes

Cyclopentadienyl-Ruthenium

Their Applications

Outlook

ru 5 c 5 r 5 mecn 3 complexes
[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

ru 5 c 5 r 5 mecn 3 complexes18
[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.

ru 5 c 5 r 5 4 diene cl complexes
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

content20
Content

Introduction

Cyclopentadienes

Cyclopentadienyl-Ruthenium

Their Applications

Outlook

cp ru catalyzed c c bond formation reactions
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
reactions involving ruthenacyclopentanes
Reactions Involving Ruthenacyclopentanes

Trost, B. M.; Pinkerton, A. B. J. Am. Chem. Soc. 1999, 121, 4068.

reactions involving ruthenacyclopentane
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.

reactions involving ruthenacyclopentane24
Reactions Involving Ruthenacyclopentane

Fujiwhara, M.; Nishikawa, T.; Hori, Y. Org. Lett. 1999, 1, 1635.

reactions involving ruthenacyclopentene
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.

reactions involving ruthenacyclopentene26
Reactions Involving Ruthenacyclopentene

Trost, B. M.; Müller, T. J. J. J. Am. Chem. Soc. 1994, 116, 4985.

reactions involving ruthenacyclopentene27
Reactions Involving Ruthenacyclopentene

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

reactions involving ruthenacyclopentene28
Reactions Involving Ruthenacyclopentene

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

reactions involving ruthenacyclopentene29
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.

reactions involving ruthenacyclopentadiene
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.

heteroatom additions to alkynes
Heteroatom Additions to Alkynes

Additions of Water

Trost, B. M.; Krause, L.; Portnoy, M. J. Am. Chem. Soc. 1997, 119, 11319.

heteroatom additions to alkynes32
Heteroatom Additions to Alkynes

Intramollecular Version

Trost, B. M.; Brown, R. E.; Toste, F. D. J. Am. Chem. Soc. 2000,122, 5877.

heteroatom additions to alkynes33
Heteroatom Additions to Alkynes

Additions of Halides

Trost, B. M.; Pinkerton, A. B. J. Am. Chem. Soc. 1999, 121, 1988.

heteroatom additions to alkynes34
Heteroatom Additions to Alkynes

Additions of Carboxylic Acids

Le Paih, J.; Monnier, F.; Dérien, S. J. Am. Chem. Soc.,2003, 125, 11964.

reactions involving additions of diazo compounds
Reactions Involving Additions of Diazo Compounds

Le Paih, J.; Dérien, S.; Özdemir, I.; Dixneuf, P. H. J. Am. Chem.Soc. 2000, 122, 7400.

reactions initiated by hydrometalations
Reactions Initiated by Hydrometalations

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

regioselective allylation of nuclephiles
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.

oxidative addition of allylic substrate
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

planar chiral ruthenium catalysts
Planar Chiral Ruthenium Catalysts

Matsushima, Y.; Onitsuka, K.; Kondo, T.; Mitsudo, T.; Takahashi, S.

J. Am. Chem. Soc. 2001, 123, 10405.

reactions initiated by c h bond activation
Reactions Initiated by C-H Bond Activation

Trost, B. M.; Toste, F. D. J. Am. Chem. Soc. 1999, 121, 9728.

content41
Content

Introduction

Cyclopentadienes

Cyclopentadienyl-Ruthenium

Their Applications

Outlook

outlook
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.

acknowledgement
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

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