IUF member in 2000


Prof. Pierre H. Dixneuf

Metal Complexes in Catalysis & Fine Chemistry

Green & Sustainable Chemistry

Phone : + 33 2 23 23 62 80 / @ : pierre.dixneuf[at]univ-rennes1.fr

Photos gallery

Prof. Dixneuf, Bruneau, Doucet, Darcel's groups 2008, 2009, 2010, 2011, 2012, 2013, 2014, 2017

Organometallics: Materials & Catalysis (OMC) group: 2012, 2015

Editors C. Bruneau & P. H. Dixneuf
Ruthenium Catalysts and Fine Chemistry (2004)
Metal Vinylidenes and Allenylidenes in Catalysis (2008)
Ruthenium in Catalysis (2014)
Editors P. H. Dixneuf & V. Cadierno
Metal-Catalyzed Reactions in Water (2013)
Editors P. H. Dixneuf & H. Doucet
C-H Bond Activation and Catalytic Functionalization I (2015)
C-H Bond Activation and Catalytic Functionalization II (2016)
Editors P. H. Dixneuf & J. F. Soulé
Organometallics for Green Catalysis (2019)
Publications 2011-2020
Publications 2005-2012
Dedicated paper book
Reviews and book chapters from 2004
Invited lectures


2004 2008 2013 2014
2015 2016 2019  
Research Topics
1. C-H bond activation / functionalization

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

Recent discoveries involve

- Fast modification of Phosphines and phosphine oxides via C-H bond functionalization, such as alkenylation, alkylations, dialkenylations
- With Ru(II) and Rh(I) catalysts. Applications to cross coupling C-H bond formation and Carboxylation of Aryl-halides  with CO2.
- Fast modification of 2-alkylpyridine N-oxides via functionalization of 2-alkyl chain alpha C-H bonds
- Synthesis via carbonylation of sp3C-H bonds via radical processes with Fe(II) and Cu(II) catalysts (with X F Wu & J F Soulé) for functionalization of alkanes and synthesis of esters, lactams, and cross coupling C-N bonds

We approached 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 involves
. 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, via an autocatalytic process. This is supported by
           - DFT calculations by Feliu Maseras (ICIQ Tarragona) and
           - kinetics By Anny Jutand (ENS, Paris)
. C-H bond functionalization 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 (with Franck Pozgan, Ljubjana)

Reviews on C-H bond activation and functionalization

- Ruthenium(II) Catalyzed C-H Bond Activation and Functionalization
Percia Beatrice Arockiam, Christian Bruneau, Pierre H. Dixneuf Chem. Rev. 2012, 112 (11), 5879–5918.

- sp2C-H Bond activation in water and catalytic cross-coupling reactions
B. Li , P. H. Dixneuf Chem. Soc. Rev.2013, 42 (13), 5744 - 5767

- Late Stage Modifications of P-Containing Ligands using Transition-Metal-Catalysed C–H Bond Functionalisation
Zhuan Zhang, Pierre H Dixneuf and Jean-Francois Soule , Feature Article, Chem. Commun., 2018, 54, 7265 – 7280 DOI: 10.1039/C8CC02821D

- Photoredox Catalysis for Building C−C Bonds from C(sp2)−H Bonds
Chang-Sheng Wang, Pierre H. Dixneuf, and Jean-François Soulé ; Chem. Rev. 2018, 118, 7532-7585. DOI: 10.1021/acs.chemrev.8b00077

- Functionalizations of C(sp2)–H Bonds of Heterocycles and Arenes Assisted with Photoredox-Catalysts for the C–C Bond Formation
P. H. Dixneuf, J.-F. Soulé In "Organometallics for Green Catalysis ", P. H. Dixneuf, J. F. Soulé Eds., Top. OrganoMet. Chem., Springer, 2019,Vol 63, 225 – 265. DOI : 10.1007/3418_2018_22


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.

As early publications in the field see

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

See Book Chapter :
Indenylidene-Ruthenium catalysts for Alkene Metathesis
P. H. Dixneuf, C. Bruneau in "Handbook of Metathesis, Volume 1: Catalyst Development and Mechanism", R. H. Grubbs, A. G. Wenzel Eds., Wiley VCH, Weinheim,  2nd edition, 2015, pp 389-416.

- 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.

Alkene metathesis catalysis: a key for transformations of unsaturated plant oils and renewable derivatives.
Pierre H. Dixneuf , Christian Bruneau, Cédric Fischmeister
Oil & Gas Sci. Technol., 2016, in press Dedicated to Yves Chauvin

Transformations of Terpenes via Carbon-Carbon Double Bond Metathesis
Bruneau, christian; Fischmeister, Cédric; Mandelli, Dalmo; Carvalho, Wagner; dos Santos, Eduardo; Dixneuf, pierre; Sarmento Fernandes, Luciana; Catal. Sci. Technol., 2018, 8, 3989-4004, CY-MRV-06-2018-001152.R1

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.

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

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)

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

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 reviews :
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.

Early steps of homogeneous catalysis in Rennes:  carbon dioxide incorporation, alkyne activation and ruthenium catalysis.
Pierre H. Dixneuf, Catal. Lett.,
2015, 145, 360–372


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.

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

Ruthenium   Containing   Cumulenes:   Generation of 2,3,4- Pentatrienylidene- and 3-Oxo-1,4-Pentadienyl- complexes.
A. ROMERO, A. VEGAS, and  P. H. DIXNEUF, Angew. Chem. Int. Ed. Engl., 1990, 29, 215-216.

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


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)