Cyclopentadienyl ruthenium catalysts one group of ru ii complexes l.jpg
Sponsored Links
This presentation is the property of its rightful owner.
1 / 46

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


  • 128 Views
  • Uploaded on
  • Presentation posted in: General

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.

Download Presentation

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

An Image/Link below is provided (as is) to download presentation

Download Policy: Content on the Website is provided to you AS IS for your information and personal use and may not be sold / licensed / shared on other websites without getting consent from its author.While downloading, if for some reason you are not able to download a presentation, the publisher may have deleted the file from their server.


- - - - - - - - - - - - - - - - - - - - - - - - - - E N D - - - - - - - - - - - - - - - - - - - - - - - - - -

Presentation Transcript


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


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 Complexes

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


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 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


Content

Introduction

Cyclopentadienes

Cyclopentadienyl-Ruthenium

Their Applications

Outlook


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.


C5H4R

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

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


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.


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.


C5H2R1R2R3CO2Et

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


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

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.


Content

Introduction

Cyclopentadienes

Cyclopentadienyl-Ruthenium

Their Applications

Outlook


[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(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(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


Content

Introduction

Cyclopentadienes

Cyclopentadienyl-Ruthenium

Their Applications

Outlook


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

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


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 Ruthenacyclopentane

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


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 Ruthenacyclopentene

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


Reactions Involving Ruthenacyclopentene

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


Reactions Involving Ruthenacyclopentene

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


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

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

Additions of Water

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


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 Alkynes

Additions of Halides

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


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

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


Reactions Initiated by Hydrometalations

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


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

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

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

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


Reactions Initiated by C-H Bond Activation

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


Content

Introduction

Cyclopentadienes

Cyclopentadienyl-Ruthenium

Their Applications

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

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


Thank you for your attention!


Proposed Mechanism


Ruthenium Hydride


  • Login