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  Cationic Ruthenium Allenylidene Complexes as Catalysts for Ring Closing Olefin Metathesis

Fürstner, A., Liebl, M., Lehmann, C. W., Picquet, M., Kunz, R., Bruneau, C., et al. (2000). Cationic Ruthenium Allenylidene Complexes as Catalysts for Ring Closing Olefin Metathesis. Chemistry - A European Journal, 6(10), 1847-1857. doi:10.1002/(SICI)1521-3765(20000515)6:10<1847:AID-CHEM1847>3.0.CO;2-1.

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 Creators:
Fürstner, Alois1, Author           
Liebl, Monika1, Author           
Lehmann, Christian W.2, Author           
Picquet, Michel3, Author
Kunz, Rainer3, Author
Bruneau, Christian3, Author
Touchard, Daniel3, Author
Dixneuf, Pierre H.3, Author
Affiliations:
1Research Department Fürstner, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1445584              
2Service Department Lehmann (EMR), Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1445625              
3UMR 6509 CNRS, Université de Rennes “Organométalliques et Catalyse”, Campus de Beaulieu, 35042 Rennes (France), ou_persistent22              

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Free keywords: alkenes; allenylidenes; catalysts; metathesis; ruthenium
 Abstract: A series of well accessible cationic ruthenium allenylidene complexes of the general type [(η6-arene)(R3P)RuCl(=C=C=CR′2)]+ X is described which constitute a new class of pre-catalysts for ring closing olefin metathesis reactions (RCM) and provide an unprecedented example for the involvement of metal allenylidenes in catalysis. They effect the cyclization of various functionalized dienes and enynes with good to excellent yields and show a great tolerance towards an array of functional groups. Systematic variations of their basic structural motif have provided insights into the essential parameters responsible for catalytic activity which can be enhanced further by addition of Lewis or Brønsted acids, by irradiation with UV light, or by the adequate choice of the “non-coordinating” counterion X. The latter turned out to play a particularly important role in determining the rate and selectivity of the reaction. A similarly pronounced influence is exerted by remote substituents on the allenylidene residue which indicates that this ligand (or a ligand derived thereof) may remain attached to the metal throughout the catalytic process. X-ray crystal structures of the catalytically active allenylidene complexes 3 b⋅PF6 and 15⋅OTf as well as of the chelate complex 10 required for the preparation of the latter catalyst are reported.

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Language(s): eng - English
 Dates: 1999-11-112000-05-152000-05-15
 Publication Status: Published in print
 Pages: 11
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Degree: -

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Title: Chemistry - A European Journal
  Other : Chem. Eur. J.
Source Genre: Journal
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Publ. Info: Weinheim, Germany : VCH Verlagsgesellschaft
Pages: - Volume / Issue: 6 (10) Sequence Number: - Start / End Page: 1847 - 1857 Identifier: ISSN: 0947-6539
CoNE: https://pure.mpg.de/cone/journals/resource/954926979058