IUF member since 2000

Prof. Pierre Dixneuf

Catalytic Engineering - Catalysis & fine Chemistry

Phone : + 33 2 23 23 62 80 - Fax : + 33 2 23 23 69 39

http://scienceschimiques.univ-rennes1.fr/catalyse

Photos gallery

Prof. Dixneuf and Bruneau's groups 2004, 2005, 2006, 2007

Prof. Dixneuf, Bruneau, Doucet, Darcel's groups 2008, 2009, 2010, 2011, 2012, 2013

Rennes Catalysis and Organometallics laboratory 2006

Organometallics: Materials & Catalysis (OMC) group: since 2012


Souvenirs from Rennes ICOMC2008 July 13-18, 2008
International Conference on OrganoMetallic Chemistry

http://icomc23.univ-rennes1.fr/


Books


Editors C. Bruneau and P. H. Dixneuf

Ruthenium Catalysts and Fine Chemistry

Metal Vinylidenes and Allenylidenes in Catalysis

Editors
P. H. Dixneuf & V. Cadierno

Metal-Catalyzed Reactions in Water

 

 

. Our objectives aim at new development of organometallic catalysis, at the selective activation of simple molecules and inert bonds to create new synthetic methods, with environment friendly reagents, under mild conditions and with atom economy and to the synthesis of target molecules or materials of industrial interest.

. To achieve this goal the team works at the interface of Organometallics, coordination chemistry and catalysis, for the design of new active molecular metal catalysts especially ruthenium catalysts, the characterisation of catalysis intermediates and the understanding of catalytic transformations.

Research Topics

1. C-H bond activation and functionalisation

2. Alkene metathesis and renewables, plant oils transformations

3. Catalysis for selective processes and fine chemistry

4. Carbon-rich organometallics

Cooperations

Reviews and book chapters from 2004

Publications 2013
Publications 2012
Publications 2011
Publications 2010
Publications 2005 -2012

Research Topics

1. C-H bond activation / functionalisation

The activation/functionalization of usually inert C-H bonds to reach new cross-coupled C-C bonds is currently our main objective.

We approach this problem by the use of easy to make and often air and water stable ruthenium(II) catalysts, especially Ru-carbonate and Ru-carboxylate catalysts. It involved:
. the direct arylation of functional arenes and heterocycles with (hetero)aryl chlorides
. the initial C-H bond activation via C-H bond deprotonation by coordinated ligand carbonate or external carboxylate and Ru(II) site. This is supported by
- DFT calculations by Feliu Maseras (ICIQ Tarragona) and
- kinetics By Anny Jutand (ENS, Paris)
. C-H bond functionalisation in green solvents and dialkylcarbonates as solvents
. C-H bond activation and arylation with aryl chlorides in water
. oxidative alkenylation of functional arenes with olefins with addition of Cu(II) catalysts
. the synthesis of polyheterocyclic derivatives and polypodal ligands


2. Alkene metathesis catalysts and applications from plant oils

. Carbon-rich ruthenium catalysts for olefin metathesis, based on ruthenium - allenylidene Ru=C=C=CR2 , the precursors of active ruthenium-indenylidene catalysts and other metathesis catalysts: Ring Closing Metathesis (RCM), catalytic synthesis of heterocycles and fluorine containing derivatives, transformation of natural products and ROMP Polymerisations.

Highly Active Catalysts in Alkene Metathesis : First Observed Transformation of Allenylidene into Indenylidene via Alkenylcarbyne - Ruthenium Species
R. Castarlenas, C. Vovard, C. Fischmeister, P. H. Dixneuf
Angew. Chem. Int. Ed. 2003, 42, 4524-4527

Allenylidene to Indenylidene Rearrangement in Arene-Ruthenium Complexes: a Key Step to Highly Active Catalysts for Olefin Metathesis Reactions
R. Castarlenas, C. Vovard, C. Fischmeister, P. H. Dixneuf
J. Am. Chem. Soc. 2006, 128, 4079-4089

. Alkene metathesis and renewables catalytic transformations of plant oil derivatives into nitrogen containing and bifunctional products.
Synthesis of linear aminoacids via cross-metathesis of unsaturated fatty esters or nitriles, with acrylonitrile or acrylates and tandem catalytic hydrogenation.



3.
Catalysis for selective processes and fine chemistry: Catalytic transformations of alkynes and development of ruthenium catalysts

. New selective catalytic combinations of simple molecules with atom economy and clean processes.
. Selective catalytic formation of C-C bonds via oxidative couplings of alkynes , diynes and enynes with electron rich Ruthenium(II) catalysts Cp*RuXLn.
. Selective syntheses of fluorinated molecules via activation and cyclisation of fluorinated amino acids or phosphonates.in cooperation with Prof S. Osipov, Ineos Moscow.(PICS, GDRI)

See review
Cp*RuCl(COD) in Catalysis : a Unique Role in the Addition of Diazoalkane Carbene to Alkynes
C. Vovard- Le Bray, S. Dérien, P. H. Dixneuf
C. R. Acad Sciences (2010) 13, 292-303

. Catalytic addition of carbenes to alkynes and enynes: This topic is now developed by Dr Sylvie Dérien, Associate professor

. Metal-vinylidenes in catalysis

. Anti-Markovnikov additions to the terminal alkynes: catalytic synthesis of enol esters, vinylcarbamates, hydrophosphination of alkynes.
. Characterisation of metal-vinylidenes, allenylidenes intermediates.

See review
Metal vinylidenes and allenylidenes in catalysis. Applications in anti Markovnikov additions to terminal alkynes and alkene metathesis C. Bruneau, P. H. Dixneuf
Angew. Chem. Int. Ed., 2006, 45, 2176-2203


4. Novel Carbon-rich organometallics and catalyst models

Novel highly unsaturated organoruthenium systems containing carbon-rich chains have been prepared for the discovery of new physical properties, the building of organometallic monomers, communication through carbon-rich bridges, and as models of ruthenium based catalysts, especially vinylidene- and allenylidene- ruthenium catalysts.

The stoichiometric activation of functional alkynes and polyynes leads to mono- and poly-vinylidenes Ru=C=CHR and allenylidenes Ru=C=C=CR2, complexes higher metallacumulenes Ru=(C=)nCR2, bimetallic systems with carbon-rich bridges, multipodal polyynes and polymetallic metal complexes.

See review: Ruthenium-allenylidene complexes and their specific behaviour.
S. Rigaut, D. Touchard, P. H. Dixneuf
Coord. Chem. Rev., 2004, 248, 1585-1601.


This topic, initiated with prof Daniel Touchard, is now developed by Stéphane Rigaut in Rennes.


Funding

Institut universitaire de France (IUF),
CNRS, Ministère de l'Enseignement Supérieur et de la Recherche,
University of Rennes, Région Bretagne,
European Union (Marie Curie, IDECAT Network),
Oril Industrie, IFP, Firmenich, Arkema
ANR (National Agency for Research