Ionic Liquids and Catalysis

Applied Catalysis A: General 373 (2010) 156
Contents lists available at ScienceDirect
Applied Catalysis A: General

journal homepage: www.elsevier.com/locate/apcata
Review
Ionic liquids and catalysis: Recent progress from knowledge to applications

H. Olivier-Bourbigou *, L. Magna 1, D. Morvan 2
IFP LYON, Departement Catalyse Moleculaire, Rond-point de lechangeur de Solaize, BP3, 69360 Solaize, France
A R T I C L E I N F O
A B S T R A C T
Article history:
Received 20 May 2009
Received in revised form 11 September 2009
Accepted 6 October 2009
Available online 12 October 2009
This review gives a survey on the latest most representative developments and progress concerning ionic
liquids, from their fundamental properties to their applications in catalytic processes. It also highlights
their emerging use for biomass treatment and transformation.
2009 Elsevier B.V. All rights reserved.
Keywords:
Ionic liquids
Biphasic catalysis
Supported Ionic Liquid Catalysis (SILC)
Task specic ionic liquids (TSIL)
Protic ionic liquids (PILs)
Thermoregulated ionic liquids
Biomass
Lignocellulose
Cellulose
Contents
1.
2.
General introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Ionic liquids: properties, evolution and next generations . . . . . . . . . . . . . . . .
2.1.
Properties of ionic liquids. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2.
A widening range of ionic liquids available. . . . . . . . . . . . . . . . . . . . . .
2.2.1.
General remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2.2.
Protic ionic liquids (PILs). . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2.3.
(Multi)-functional ionic liquids . . . . . . . . . . . . . . . . . . . . . . . .
2.2.4.
Chiral ILs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2.5.
Switchable-polarity solvents (SPS) . . . . . . . . . . . . . . . . . . . . .
2.2.6.
ILs at the frontier between organic and inorganic materials.
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3
3
3
5
5
7
8
10
11
11
Abbreviations: IL(s), ionic liquid(s); [BMI]+, 1-butyl-3-methylimidazolium; [BMMI]+, 1-butyl-2,3-dimethylimidazolium; [MMI]+, 1-methyl-3-methylimidazolium; [HMI]+, 1hexyl-3-methylimidazolium; [OMI]+, 1-octyl-3-methylimidazolium; [AMI]+, 1-allyl-3-methylimidazolium; [AEI]+, 1-allyl-3-ethylimidazolium; [MI]+, 1-methyl-3-Himidazolium; [BMPy]+, N-butyl-3-methylpyridinium; [BPy]+, N-butylpyridinium; [PrMI]+, 1-propyl-3-methylimidazolium; [BMP]+, N-butyl-N-methylpyrrolydinium;
[PMP]+, N-propyl-N-methylpyrrolidonium; [NTf2], bis(triuoromethylsulfonyl)amide (CF3SO2)2N; [OTf], triuoromethylsulfonate CF3SO3; [OMs], mesylate CH3SO3;
[Fm], formate HCOO; [Ac], acetate CH3COO; TPPTS, triphenylphosphine trisulfonate sodium salt; TPP, triphenyphosphine; PEG, poly(ethylene glycol); LAB, linear alkyl
benzene; COD, 1,3-cyclooctadiene; SWNT, single wall carbon nanotube; TSIL, task specic ionic liquid; SILP, supported ionic liquid phase catalysis; PSIL, polystyrene
supported ionic liquids; SPS, switchable polarity solvent; PTC, phase transfer catalysis; LSER, linear solvation energy relationship; MD, molecular dynamics; DFT, density
functional theory; QSAR, quantitative structureanalysis relationship; HDS, hydrodesulphuration process; MAO, methylaluminoxane; CIL, chiral ionic liquid; PIL, protic ionic
liquid; DMSO, dimethylsulfoxide; DMAc, dimethylacetamide; PPN, bis(triphenylphosphorylidine)ammonium cation; DBU, 1,8-diazabicyclo-[5.4.0]-undec-7-ene; DABCO,
1,4-diazabicyclo[2.2.2]octane; REACH, registration, evaluation and authorisation of chemicals; EINECS, european inventory of existing commercial chemical substances;
EXAFS, extended X-ray absorption ne structure; ESI-MS, electrospray ionization-mass spectrometric; NOESY, nuclear overhauser enhancement spectroscopy; HOESY,
heteronuclear version of the NOESY experiment; ROESY, rotating frame overhauser effect spectroscopy.
* Corresponding author. Tel.: +33 4 78 02 28 89; fax: +33 4 78 02 20 66.
E-mail addresses: helene.olivier-bourbigou@ifp.fr (H. Olivier-Bourbigou),
lionel.magna@ifp.fr (L. Magna), didier.morvan@ifp.fr (D. Morvan).
1
Tel.: +33 4 78 02 28 86; fax: +33 4 78 02 20 66.
2
Tel.: +33 4 78 02 38 74; fax: +33 4 78 02 20 66.
0926-860X/$ see front matter 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.apcata.2009.10.008
H. Olivier-Bourbigou et al. / Applied Catalysis A: General 373 (2010) 156
2.3.
3.
4.
5.
6.
7.
8.
Latest advances in the preparation and purication of ILs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

2.3.1.
The different ways of ILs preparations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.3.2.
Purication of ILs and analysis of trace impurities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Structure and self-organisation of ILs at the supramolecular level . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.1.
Solvent properties and solvent effect. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.2.
Structure and organisation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.3.
Toward a mesoscopic organisation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.4.
Solute-ILs interactions: what impact on organic reactions? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.4.1.
Interaction with water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.4.2.
Interaction with aromatic hydrocarbon. Clathrate behaviour . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.4.3.
Interaction with chiral substrates: induction of chirality? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.4.4.
Interaction with acid and base: toward new scale of acido-basicity . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.5.
Molecular modelling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
How the ILs can affect the catalytic reactions pathway?. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.1.
Some unexpected effects of ILs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.1.1.
Effect of ILs impurities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.1.2.
Effect of water and acidic protons . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.1.3.
Effect of bases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.1.4.
ILs as additives: surprising effect! . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.2.
When ionic liquids are involved in the formation of metal complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.2.1.
Complex formation involving anions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.2.2.
Complex formation involving cations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.3.
ILs specially designed for catalysis. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.3.1.
Change in mechanism pathway by stabilisation of charged transition state, active species or ligands
4.3.2.
Solvent for non-charged catalysts. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.3.3.
Solvent/stabiliser for nanoparticles. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.4.
Ionic liquids as medium for in situ spectroscopic investigations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.5.
Removing sulfur from renery streams . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Concepts for using ILs in homogeneous catalysis. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.1.
Multiphasic IL systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.1.1.
Some challenges and opportunities of multiphasic systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.1.2.
Use of scCO2 as the transport vector for substrates and products . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.1.3.
Demonstration of continuous catlytic performances . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.2.
Supported ionic liquid phase system (SILP). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.2.1.
ILs supported on solid inorganic solid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.2.2.
ILs supported on hybrid organicinorganic material . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.2.3.
ILs supported on organic polymers. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.3.
Switchable polarity solvents. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.4.
Thermoregulated ILs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.5.
Phase transfer catalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Overview of industrial applications and economic issues . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
6.1.
Selected examples of industrial/pilot scale applications of ILs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
6.1.1.
Dimerization and oligomerisation of olens: IL as solvent and Ni-co-catalyst. . . . . . . . . . . . . . . . . . . .
6.1.2.
Friedel-Crafts alkylation and acylation of aromatic hydrocarbons: IL as solvent and catalyst. . . . . . . .
6.1.3.
Alkylation of olens with isobutane: IL as solvent and acid catalyst . . . . . . . . . . . . . . . . . . . . . . . . . . .
6.1.4.
Chlorination and uorination reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
6.1.5.
Ether cleavage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
6.1.6.
Acid scavenging . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
6.1.7.
Hydrosilylation: IL as solvent and nanoparticle stabiliser . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
6.1.8.
Isomerisation: IL as a solvent . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
6.1.9.
Methanol carbonylation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
6.1.10. Other examples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
6.2.
Main process engineering challenges and issues. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
6.2.1.
IL stability, lifetime and recyclability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
6.2.2.
Safety and environmental issues: . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
ILs application in the biomass transformation into fuel and chemicals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
7.1.
Processing of lignocellulosic and cellulosic materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
7.1.1.
Direct solvent for dissolution of cellulose and sugars . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
7.1.2.
Treatment of lignocellulosic materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
7.2.
Applications of the use of ILs in the dissolution of ligno-cellulosic materials . . . . . . . . . . . . . . . . . . . . . . . . . . . .
7.2.1.
An improvement in the analysis of lignocellulosic material . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
7.2.2.
Transformation of poly-saccharides in sugars using ILs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
7.2.3.
Catalytic transformation of sugars . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
7.3.
Transformation of vegetable oils . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
7.3.1.
Transesterication of triglycerides: biodiesel production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
7.3.2.
Methyloleate metathesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
General conclusion and perspectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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51
1. General introduction
Ionic Liquids (ILs) have attracted rising interest in the last
decades with a diversied range of applications (Fig. 1). The types
of ionic liquid available have also been extended to include new
families and generations of ionic liquids with more specic and
targeted properties. This expanding interest has led to a number of
reviews on their physico-chemical properties, the design of new
families of ionic liquids, the chemical engineering and the wide
range of arrangements in which ILs have been utilised (liquid
phase, multiphase, immobilized on supports, . . .) and pilot or
industrial developments [1].
Why ILs have attracted so much attention in the last few decades?
In addition to the fact that they are now commercially available,
there is a better understanding of the effect of ionic liquids
(chemical and physical properties as well as engineering uids).
Consequently, ionic liquids have been used more widely and
efciently, with better control over the overall process. The
introduction of structural functionalities on the cationic or anionic
part has made it possible to design new ILs with targeted
properties [2]. More recently, ILs appear to be the subject of
fundamental publications aimed at improving the understanding
of these solvents, predicting their physico-chemical properties and
publications describing their use in increasingly diverse applications such as sensors, fuel cells, batteries, capacitors, thermal
uids, plasticizers, lubricants, ionogels, extractants and solvents in
analysis, synthesis, catalysis and separation, to name just a few.
Some new applications, such as energetic compounds or pharmaceutical ILs, are still emerging. ILs can be used as more than just a
alternative green solvents. They differ from molecular solvents
by their unique ionic character and their structure and organisation which can lead to specic effects. They are tuneable,
multipurpose materials.
When reading papers on ILs, one of the key words is diversity.
Diversity of anioncation combinations, diversity of modes of
preparation, modes of purication and nature of impurities
(quality), diversity of properties, diversity of mode of use, diversity
of applications. This is one of the reasons why it is so difcult to
make generalisations about their physical properties or their use.
The contribution ILs make to homogeneous catalysis has more to
do with the enhancement of catalytic performances (activity,
selectivity or new chemistry) and the possibility of catalyst
separation and recycling by immobilization in the IL-phase than
with environmental concerns. They can act as solvents, as
multifunctional compounds like solvents and ligands, solvents
and catalysts, stabilising agents for the catalysts or intermediates.
The performance of an IL will strongly depend on the technology in

which it is implemented. They can be utilised in very different
ways: homogeneous, multiphase, heterogeneous, in bio transformations or in organo-catalysis. They play a specic role in all these
approaches.
Even more than diversity, another keyword for the end-user is
prediction. When will it be possible to move ahead to rational design
of ionic liquids? Is it possible to predict which ionic combination
results in a given set of properties? Most work towards understanding and knowledge has been achieved on imidazolium
cations, certainly the most popular cation but not the only one.
New families of ILs with various other cations have been developed
these last decades. ILs are not trivial. They are generally composed
of asymmetric and exible ions, with components of highly
different sizes and shapes, and involve different types of dominant
interactions. Theoretical treatment and interpretations are complicated. However, it is important to have a better understanding of
neat ILs properties, and their properties and interactions with
other species such as molecular species or metal complexes to
better understand their role in catalysis.
The aim of this review is not to provide an exhaustive list (or state
of the art) of the wide range of catalytic reactions occurring in ILs.
Several good, recent reviews have already illustrated that point
(Table 1). This review focuses mainly on recently published material.
We have restricted ourselves to give a survey on the latest, most
representative developments and progress on ionic liquids and
catalysis. This review also covers the different aspects of ILs, from the
knowledge we have of these media to the use of their properties for
catalysis, catalytic processes and engineering. More particularly, the
following are reported: (i) the design of new generations of ILs: the
evolutions and key events (a general history of the ILs is described by
J. Wilkes [3]). (ii) fundamental properties of ILs: structure and
organisation, IL-solute interactions, (iii) the ILs effect: how ILs can
impact the outcome of the reaction and how it is possible to control
the reaction process, (iv) the diversity of IL use in catalytic processes:
homogeneous, multiphase, heterogeneous, (v) comments on
industrial applications and commercial aspects of ILs: barriers to
overcome? (vi) key events in environmental catalysis: this last
chapter focuses on the role that ILs can play in the treatment and
transformation of bio-resources and in bio-processes.
2. Ionic liquids: properties, evolution and next generations
2.1. Properties of ionic liquids
Considering the broad range of ILs and applications [46], it is
difcult to generalise their properties and to report general
tendencies. Sometimes the authors emphasise their differences
Fig. 1. Evolution of IL generations.
4
Table 1
General reviews on ILs (from 2003 to 2008).
General (catalysis)
Task-specic ILs
ILs in catalysis
Catalysis in ILs
Homogeneous catalysis in ILs
Catalysis in ILs
Transition metal-catalysed reactions in
non-conventional media
The path ahead for ILs
Applications of ILs in the chemical industry
Catalysts with ionic tag and their use in ILs
Specic reaction/topic (catalysis)
Polymerization processes in ILs
Supported ionic liquid phase (SILP) catalysis
Oxidations of organic compounds in ILs
Functionalised imidazolium salts for TSILs
and their applications
Olen hydroformylation in ILs
Brnsted acids in ILs
Enantioselective catalysis in ILs
Asymmetric synthesis in ILs
Lanthanides and actinides in ILs
ILs in separations
Olen metathesis in ILs
Palladium-catalysed reactions in ILs
ILs towards supercritical uid applications
ILs in heterocyclic synthesis
Applications of chiral ILs
Synthesis and application of chiral ILs
Electrochemical reactions in ILs
Bio-catalysis/biomass
Biocatalysis in ILsadvantages beyond green technology
Biocatalytic transformations in ILs
ILs: Green solvents for nonaqueous biocatalysis
Chemical and biochemical transformations in ILs
Biocatalysis in non-conventional media (ILs, scFluids.)
Biocatalysis in ILs
Ionic green solvents from renewable resources
Oxidoreductase behaviour in ILs
Biotransformations and organocatalysis with ILs
Dissolution and functional modication of cellulose in ILs
Synthesis (inorganic & organic)
Metal-containing ILs and ILs crystals based on
imidazolium moiety
ILs solvent properties and organic reactivity
Application of zeolites in supercritical uids and ILs
The phosphorus aspects of green chemistry
Application of ILs in polymer science
Analysis
ILs in chromatographic and electromigration techniques
Year
Ref.
2004
2004
2006
2007
2007
2007
[4]
[5]
[6]
[7]
[8]
[9]
2007
2008
2008
[10]
[11]
[12]
2004
2006
2006
2006
[13]
[14]
[15]
[16]
2007
2007
2007
2007
2007
2007
2008
2008
2007
2008
2008
2008
2008
[17]
[18]
[19]
[20]
[21]
[22]
[23]
[24]
[25]
[26]
[27]
[28]
[29]
2003
2003
2005
2005
2007
2007
2007
2008
2008
2008
[30]
[31]
[32]
[33]
[34]
[35]
[36]
[37]
[38]
[39]
2005
[40]
2005
2007
2007
2009
[41]
[42]
[43]
[44]
2008
[45]
and not their similarities. Some of the properties described some

years ago are now subject to controversy: e.g. electrochemical
window; long-term thermal stability (thermal stability was
certainly overestimated in the past); polarity; volatility (some
ILs are distillable under certain conditions [47]). Why all of these
conicting results? Because an evolution toward a better understanding of these media, better characterization with improved
knowledge and quantication of their impurities (ion chromatography, ICP-MS) which are well-known to affect the thermophysical properties of ILs, have been achieved in recent years. The
different experimental techniques used and the estimation of data
uncertainty may also have inuenced the discrepancies in terms of
physico-chemical properties. However, ILs have widely accepted
generic properties. They consist entirely of ions (Scheme 1). For
example, in [BMI][PF6] which melts at 12 8C, the ionic concentration is 4.8 mol/L. The melting point of ILs should be less than
100 8C, even if this is an arbitrary temperature limit, and their
ionicity should be >99%. All these generic properties have been
described in open literature and can be easily found in a good

database (e.g. ILThermomanaged by the US National Institute of
Standards and Technologies) [48]. They will not be reported in
detail in this reviewonly a list of critical remarks is given below.
Melting point: Data must be considered with caution as the
melting point of many ILs may be uncertain as they can undergo
supercooling and because of the potential presence of impurities.
Volatility: For typical ILs, normal boiling temperatures (Tb), which
correlate with their vapour pressure at 1 atmosphere, cannot be
experimentally determined as ILs decompose at a lower
temperature. It has nevertheless been reported that ILs can be
distilled at 200300 8C but under signicantly reduced pressure
and at very low distillation rate (<0.01 g h1) [47]. The question
is how ionic are ILs? The ionic nature (or ionicity) of ILs can
partially explain their negligeable vapour pressure in the liquid
state, which distinguishes them from molecular solvents.
Quantitative descriptions of the ionicity would be a useful
indicator for characterizing ILs. This has tentatively been done
using the effective concentration of ions [49].
Non ammability: Much of the interest for ILs has been centred on
their possible use as green alternatives to volatile organic
solvents, mainly because ILs are considered as non-volatile and
consequently non-ammable at ambient and higher temperatures. However there are many other potential solvents that
meet these criteria but that have not been subject to such
interest. It is worth mentioning that it is not because they are
non-ammable that ILs can be used near a heat source. ILs are
combustible. They even can be ne-tuned for energetic content
and replace hydrazine and its derivatives [50,51].
Thermal and chemical stability: The onset of thermal decomposition calculated from fast thermogravimetric analysis (TGA)
indicates high thermal stability for many ILs, generally >350 8C.
However, lower values are found for long-term stability which is
important to consider when ILs are used in catalytic processes.
Phosphonium ILs with [NTf2] or [N(CN)2] anions decompose
completely to volatile products in a single step. The degradation
products indicate that Hofmann elimination process and/or
dealkylation reactions occur. On the contrary, ILs based on
nitrogen cations do not decompose completely and generate char
residue (cyano groups are prone to polymerization) [52].
Conductivity and electrochemical window: ILs conductivity is an
interesting property to consider as ILs can play the role of both
solvents and electrolytes in electrochemical reactions. ILs exhibit
broad range of conductivities spanning from 0.1 to 20 mS cm1. In
general higher conductivities are found for imidazolium-based ILs
in comparison with the ammonium ones. Many factors can affect
their conductivity, such as viscosity, density, ion size, anionic
charge delocalization, aggregations and ionic motions [29]. Strong
ion-pair associations have been invoked in the case of [NTf2]
based ILs, to understand their lower conductivity in comparison
with [BF4] based ILs [53]. Concerning their electrochemical
window, it is typically found in the range 4.55 V, which is similar
to or slightly larger than that found in conventional organic
solvents, but larger than that of aqueous electrolytes. Quaternary
ammonium is generally more stable toward reduction than
imidazolium which can lead to the formation of N-heterocyclic
carbenes. The challenge here is still to design ILs with wide
electrochemical window along with good electrical conductivity.
Density: A considerable amount of data on the density of ILs are
available in the literature [54]. ILs are generally denser than
either organic solvents or water, with typical density values
ranging from 1 to 1.6 g cm3. The density of ionic liquids versus
pressure and temperature has also been modelled [55].
Viscosity: From the engineering aspect, the viscosity of ILs can
affect transport properties such as diffusion and may be an issue
Scheme 1. Main cations and anions described in literature.
in practical catalytic applications. It plays a major role in stirring,

mixing and pumping operations. The viscosity of many ILs is
relatively high compared to conventional solvents, one to three
orders of magnitude higher. For a variety of ILs it has been
reported to range from 66 to 1110 cP at 2025 8C. The design of
less viscous ILs is still a challenge for many applications [56].
Polarity: The polarity is one of the most important properties for
characterizing the solvent effect in chemical reactions [57]. It is
also the property which has probably been the most widely
discussed in the case of ILs. Why? Because there is no single
parameter and direct measurement that can characterize IL
polarity. Solvatochromic dyes can be used to determine empirical
polarity parameters but these parameters (Kamlet-Taft equation)
are probably not truly independent on the probe molecule used.
The difculty in the case of ILs is to nd a suitable soluble probe
which measures the polarity parameters as independently as
possible of the other inuences of the solvent [58,59].
Toxicity and biodegradability [50,60]: The early claims of the low
toxicity and biodegradability of ILs has often been reduced to
their negligible vapour pressure which, of course, is not realistic.
It has been conrmed that commonly used ionic liquids are not
easily biodegradable. But should this be a major limitation to
their use on industrial cases?
Surface tension: It has been the topic of a relatively minor number
of studies. ILs have relatively moderate surface tensions
compared to organic solvents [61].
For industrial implementation, some IL properties must be investigated under real process conditions. A screening of some properties
such as compressibility has been examined under long-term
conditions and under high pressure [62]. How can they be compared
to conventional solvents? Fig. 2 gives a tentative qualitative description
of ILs compared to alternative solvents, in terms of polarity and
volatility.
chemical properties. Protic ILs and Brnsted and/or Lewis ILs

can be used as acid catalysts and solvents. Basic ILs have also
recently been reported as playing a dual role of solvent and
base-catalyst with a particular interest and potential for
cellulose acetylation [63]. ILs bearing a function (phosphorous,
nitrile, imine, amine, alkyne) have been applied as both ligands
and supports for immobilizing and recycling transition metal
homogeneous catalysts [64] or as protective agents and
solvents for the stabilisation of metal nanoparticles. ILs
supported organo-catalysts (such as proline as a chiral catalyst
in asymmetric synthesis) have been developed to improve the
recovery of the catalyst which is often used in substantial
quantities [65]. Chiral ILs, such as solvents and chiral inducting
agents, have been modied in various ways, the chirality being
incorporated on the cationic or anionic part of the ILs.
(2) The tuneabiliy of combinations of cations and anions and the
possibility to achieve modication of the cation and/or the
anion part offer access to ILs with targeted properties. For
examples, the hydrophilicity/hydrophobicity exibility, the
decrease of ILs viscosity, and the increase of ILs stability are still
challenging targets. [NTf2] and [N(CN)2] anions already
appear as good candidates to get ILs with lower viscosity. The
replacement of alkyl group on the imidazolium by more
exible ether group was also a way to decrease both viscosity
and melting point (Scheme 2). The replacement of alkyl groups
by oligoether groups has been shown to decrease the ionic
liquids viscosity signicantly. This effect has been demonstrated both for substituents at the anion (such as sulfate) [66]
2.2. A widening range of ionic liquids available

2.2.1. General remarks
The number of ILs has expanded exponentially recent years. A
compilation of all the described cations and anions is not possible.
The main reviews can provide an overview. Many diverse
motivations can explain the design of new IL families. Some of
them are described in the following points.
(1) A great deal of attention has been devoted to (multi)functional
ILs (often termed task-specic ILs) aimed at using synergic
Fig. 2. Typical polarity and volatility characteristics of alternative solvents.
Scheme 2. ILs with targeted properties (decrease viscosity and density).
Scheme 3. New methimazole based ILs.
and for substituents at the cation (such as PEG-functionalised

imidazolium dialkylphosphates) [67]. Novel ILs with Si
substituted cations were also reported and present a reduction
of viscosity thanks to a more exible side chain than an ether
[68]. This may be important since mass transfer may be
important, reaction rate can be increased by reducing the
viscosity of the ILs [69].
is replaced with ILs based on dicyanamide anions, have been

proposed. It is expected that these ILs can be ne-tuned for better
energy content and physical properties [51]. ILs such as
dialkylimidazolium formate were produced as liquids having
strong hydrogen bond accessibility. They are good solvents for
polysaccharides dissolution [77] under mild conditions and high
concentrations (Section 7.1.1).
There has been an increased interest for ILs that present better
inertness under reaction conditions. The hydrolysis of [PF6] or
[BF4] anions to generate HF in situ has been the object of
numerous reports. Reactions catalysed by protic acids have often
been described in [PF6] based ILs, probably thanks to the presence
of HF. The formation of transition metal uoride under certain
conditions has also been observed [70,71]. The ionic liquid based
on the [(C2F5)3PF3] anion has been recently proposed as a more
chemically stable alternative to [PF6] [72].
The activation of the C(2)-H of the imidazolium to lead to the
N-heterocyclic carbene (NHC) in presence of base is also largely
described [73]. Consequently, increased interest has been found
in phosphonium ILs because of their higher stability under
basic conditions, such as in Grignard reactions [74]. To protect
the acidic C(2)-H, 2-methylimidazole based ILs are often used.
By analogy, methimazole based ILs have been described in
which the C(2) proton is replaced by a thiol linkage (Scheme 3)
[75].
The latest applications of ILs concern ILs with biological
properties (Scheme 4) [76]. Hypergolic fuels in which hydrazine
(3) Cost and biodegradability have also been a main concern and
new families of ILs derived from renewable feedstock or from
low cost starting materials have been described (Scheme 5).
These Bio-ILs are entirely composed of biomaterials [78]. An
example is given by the development of the deep eutectic
mixtures liquid systems based on chloline chloride [79] for
which the qualication of ionic liquids is still the subject of
controversies. Choline can be used as alternative cation in
combination with suitable anion to generate ILs (choline
salicylate melts at 50 8C and was described in 1960). The
physical properties (viscosity, melting point, thermal stability,
polarity) of different carboxylate anions such as acetate, tartrate,
lactate, succinate, glycolate, maleate coupled with choline cation
have been described. Surprisingly glycolate presents a Tm of
38 8C. The thermal stability range of the series is 183223 8C
[78]. The maleate gives moderate viscosity. Other interesting ILs
based on choline cations have been prepared by direct
neutralisation of choline hydroxide with different aromatic or
cyclic aliphatic carboxylic acids (Scheme 6). Surprisingly, some
of these ILs show low Tg and Tm. The biodegradability properties
Scheme 4. Examples of ILs with targeted functions.
Scheme 5. Cost-effective ILs.
of these ILs have been reported [80]. Very recently, it was shown
that the incorporation of ester side chain moiety on pyridinium
or nicotinium cation could lead to biodegradable ILs contrary to
the pyridinium analogues ILs [81].
(4) New materials have been developed using imidazolium as
backbone to access to functional silica gels or carbon nanotubes
with exible properties [82]. The IL is immobilized on the solid
support by covalent bonds generally between the silyl group
and the imidazolium cation. The immobilization of metal ions
on silica surface offers a novel class of materials where the
environment of the metal is comparable to that found in of the
type [BMI]2[MX4] [83].
Scheme 6. Bio ILs.
(5) ILs recyclability [84] becomes one of the main issues when
process developments are envisioned: distillable ILs (under
relatively normal pressure and temperature conditions) or ILs
presenting low thermal stability have been designed. These ILs
can contain a weakly basic anion and a cation formed from a
tertiary amine and an exchangeable proton (Scheme 7). By
distillation, the neutral acid or base (if volatile enough) can be
separated from the ionized species. They can subsequently be
recombined to reform the IL. There is a vast number of cation
anion combination of such protic ILs. Carbamate based ILs form
another class of distillable ILs (see switchable solvents). Each
application requires specic properties, there is no ILs that can
satisfy all of them. We will focus here on the last developments.
2.2.2. Protic ionic liquids (PILs)
While one of the rst IL, described in 1914 by Walden [85], was of
the protic type [EtNH3][NO3] (with a mp = 12.5 8C, described in
nearly all reviews on ILs!), aprotic ILs largely dominate the open
literature due to their inertness relative to organometallic compounds and their potential of applications, particularly in catalysis.
However, there has been a resurgence of interest for these Protic ILs
essentially because of their great potential for proton transfer
applications in fuel cell technologies. A review was written by Poole
including the use of these Protic ILs in chromatography [86]. Some of
these ILs present low melting points (well below 100 8C) and high
conductivities (over 102 S cm1 at 130 8C) [87]. Most of the nonprotic ILs are synthesised by transferring an alkyl group to the basic
nitrogen site through SN2 reactions. Protic ILs are formed through
direct proton transfer from a Brnsted acid to a base (or a Brnsted
Scheme 7. Protic ILs synthesised by direct protonation (X = [NTf2], [CF3SO3], [CF3CO2], [CH3SO3], [HCOO], [HSO4], [H2PO3]).
base). They present the advantage of being cost-effective and easily

prepared as their formation does not involve the formation of
residual by-products. Examples of Protic ILs are given in Scheme 7
[88,89]. Many of these Protic ILs involve very strong acids, such as
HNTf2, and hence the equilibrium is heavily shifted to the right thus
producing ILs as completely ionic salts. These ILs are generally liquid
at room temperature.
NMR measurements show that the NH proton is not labile,
which tends to indicate that these ILs cannot be really considered
as Brnsted acids [90]. The acidic properties of these ILs could
rather be ascribed to the presence of residual acid in the medium
coming from the synthesis. The purity has to be checked properly
by a more sensitive mean than NMR. In the case of weak acid, such
as acetic acid, the neutralisation reaction will reach a point of
equilibrium. The complete or not ionicity of these mixtures have
been discussed by different groups and the challenge is still to
provide an unambiguous measurement of this degree of ionization,
since the values for equilibrium constants are not known under
non-aqueous conditions [91]. These liquids can probably be best
described as liquid mixtures of ionic and neutral species. It has
been suggested that to be classied as ILs, according to a formal
denition, the products must be >99% ionized, and thus a careful
selection of acids and bases (based on pKa) is required [92].
The case of protic bases (such as dialkylamines) has also been
studied (Scheme 8). In 1:1 mixtures, the boiling point is usually
much higher than the average value of the acid and the base
precursors. This may suggest that signicant and fast proton
transfer between acid and base molecules occurs [93].
One can predict a growing interest in near future in ILs with
dissociable protons not only as potential solvents but also for
their different properties and behaviours, their ability to form Hbonds (proton donor and acceptor) and their use to build a
hydrogen-bond network [94]. However, a limitation of these
protonated imidazolium salts is that they decompose at relatively
Scheme 8. N,N-dimethylethanolammonium formate ILs.
low temperatures compared with their alkylated homologues

while this property has been advanced as an advantage for
recycling.
Another interesting example of Protic ILs is based on the use of
hydrophilic monodispersed and hyperbranched dendrimer polymers base such as polyamidoamine (Fig. 3). Protonation of this
polymer with Brnsted acid, followed by metathetic exchange of
anion with [NTf2] leads to the formation of an hydrophobic IL the
low Tm of which being ascribed to the exible nature of the
dendritic backbone (Tm = 2.5 8C). Conductivity and thermal
degradation (near 350 8C) were determined. This IL, beside its
use as proton conductive electrolytes, could be well suited for
particles encapsulation [95].
Brnsted ILs can be classied besides the PILs. An overview on
these ILs incorporating carboxylic esters and acid groups and their
zwitterionic counterpart has been written in 2004 [96]. Another
recent review gives an overview on the different Brnsted ILs and
their applications in organic synthesis and catalysis [18].
2.2.3. (Multi)-functional ionic liquids
Recently, ILs based on different cations and anions bearing
functional groups have been the object of several recent reviews
[12,16,96100].
2.2.3.1. Solvent and acid or base function. Acidic and basic ILs
represent new classes of ILs (Scheme 9). The acid or basic function
can be attached either on the anion, either on the cation [63]. ILs
Fig. 3. ILs based dendrimer polymers base (reprinted with permission from [95]. Copyright 2009 American Chemical Society).
Scheme 9. Acid and basic ILs.
containing polynuclear metallic anions such as chloroaluminates,

have been known for a long time for their potential Lewis acidity
and superacidity in presence of protons. They have been extended
to other polynuclear anions that are stable in presence of water and
oxygen such as chloroferrate or chlorozincate. The chloroferrate
anions have been associated with [NEt3H]+ to generate cheap and
easy to make acidic catalysts. Interestingly, Brnsted acidity can
also be introduced by addition of Brnsted acids such as HF or HCl
into halide based ILs. This is a way to reduce the volatility of the
acid by supporting it in the ILs through the formation of X(HX)n
type anion ([X] = [F] or [Cl]) [101]. The species [HCl2],
[H2Cl3], and [H3Cl4] are also known to form when Brnsted
acids are dissolved in chloride-rich chloroaluminate ionic liquids
[102,103]. But some leaching of the acid in presence of an organic
phase can be expected.
Alkane sulfonic or carboxylate acid groups have been covalently
tethered to different cations such as imidazolium, benzimidazolium [104], pyridinium [105], ammonium, or phosphonium
tethered sulfonic acid tosylate [106]. An interesting IL has been
described with the acidity linked to a quaternary ammonium
([Me3N-(CH2)2-CO2H][X]), associated with the [NTf2] anion, this
compound has a melting point of 57 8C. It is known to solubilise
metal oxide [107].
The hydrogen atom in the C(2)-position of the dialkylimidazolium cation can also be proposed as source of acidity. For example, Nheterocyclic carbenes have been electrogenerated by cathodic
cleavage of the C(2)-hydrogen bond of imidazolium-based roomtemperature ionic liquids. These carbenes proved to be quite stable
bases that can be used for the deprotonation of bromoamines [108].
Basic ILs have been less developed than acidic ones. Amine
organic bases have been tethered to IL cations. These functional ILs
were rstly synthesised to capture CO2 [109,110]. Mono-charged
diamine based ILs which incorporate Lewis basicity site (DABCO
type) on the cation with both thermal stability and low melting
point can be obtained when associated with [NTf2] anion (Scheme
10) [111,112].
One interesting concept has been described to switch the
basicity of ILs. This is achieved by using amino-group containing
ILs, either on the cation, either on the anion (Scheme 11). By adding
CO2 pressure to the solutions, the basicity can be signicantly
reduced. The basicity can be repeatedly recovered by removing CO2
by bubbling N2 to the ILs. This simple and reversible method could
have potential applications in different elds [113]. Further, some
basic ILs containing biodegradable components, including ILs
derived from natural amino acids have been developed [113].
Finally, ILs synthesised by the reaction of [RMI][OH] with
different poly-acids such as oxalic acid, malic acid, phthalic acid,
tartaric acid. can be mentioned. According to the quantity of acid
added, these ILs can display a certain acidity level. They have been
used as buffers in pH sensitive catalytic reaction for controlling the
acidity in non-aqueous media. The interest is that they may
present solubilisation properties in organic solvents [114].
In the case of these acid or basic ILs, it is worth emphasising that
the presence of impurities, such as water, halide, organic bases or
acids or traces of solvents, mainly coming from the synthesis of the
Scheme 10. Examples of basic ILs.
Scheme 11. Example of switchable Lewis basic ILs.
10
Scheme 12. Functional ILs as ligands and supports for transition metal complexes.
ILs, can dramatically modify their acido-basic properties. The

determination of the level of acidity of these ILs has most of time
not been determined which can sometimes lead to misunderstanding in the role of the ILs.
2.2.3.2. Full-size image.
Solvent and ligand. In multiphase catalysis, the main challenge is to
recycle the catalyst, to maintain the transition metal in the IL phase
and to prevent its loss by leaching on workup. The number of
described tagged ligands is huge and their eld of applications
cover nearly all catalytic reactions. Great progress, especially in the
organic synthesis of tagged ligands, has been achieved (Scheme
12). Ionic phosphorus ligands are the subject of ongoing research
for different catalytic reactions. ILs open a new eld for the use PO
based ligands, rarely used in water because of their sensitivity to
hydrolysis. Almost a dozen of cationic phosphite ligands have been
recently described, some of them could have been produced on
quite large scale [115].
2.2.4. Chiral ILs

The number of publications dealing with chiral ILs (CILs)
grew rapidly [28]. The source of chirality can be provided
either on the cation, on the anion or both on anion and cation
(Scheme 13).
A large range of CILs have been prepared based on chiral aminoacids anions and ammonium, imidazolium and phosphonium
cations [116,117]. Beside imidazolium, guanidinium cations have
also opened the opportunity to create a new family of chiral ILs
based on natural chiral anions. The applications of these CILs can be
found in asymmetric catalysis, but also in spectroscopic and
chromatographic applications. In asymmetric synthesis, it is often
believed that CILs can be used as chiral solvents and as sole inducer
of chirality due to their polymer-like behaviour and potential high
degree of organisation. However, very few results are reported
which demonstrate such potential. The rst result was reported by
the group Vo-Thanh in the Baylis-Hillman reaction [118] The IL
used is based on the chiral ephedrinium cation (Scheme 14). The
Scheme 13. Examples of chiral ILs.
11
Scheme 17. Two-steps formation of Ag based hydrophobic ILs (L = olen or

diolen).
Scheme 14. Chiral ephedrinium based ILs.
2.2.6. ILs at the frontier between organic and inorganic materials

2.2.6.1. Inorganic cations. A new methodology to synthesise ILs is
by complexing inorganic cation such as Ag or Zn with neutral
organic ligands such as olen, amide and amine compounds
(Scheme 17). The associated anion can be subsequently changed by
metathesis reaction, such as [NTf2], to generate less viscous and
hydrophobic ILs (mp < 10 8C for most of the ILs studied, high
conductivity and low viscosity but low decomposition temperature for [Ag(olen)x][NTf2] with the olen being 1-hexene, 1pentene, 1-isoprene or ethylene). For example, [Ag(1-butene)2][BF4] has a melting point of about 37.5 8C. It is well-known
that unsaturated hydrocarbons can form reversible p-complexes
with the metallic cations (Ag+ or Cu+). In these new ILs, silver is not
introduced as a solute but is in the structure of the ILs itself, thus
making its content quite high. These ILs have been applied for
separation process of olen/parafns. They combine the properties
of ILs, liquid and solid membranes [123].
Scheme 15. Example of silica supported CIL.
hydroxy functionality of the cation plays an important role in the

enantioselectivity.
IL-supported chiral ligands are also largely described. These ILs
have tentatively been supported on inorganic materials but very
often with a loss of enantioselectivity. For example, highly ordered
mesoporous functional organosilicas incorporating chiral camphorsulfonamide entities were synthesised by a hydrolysis
polycondensation involving chiral imidazolium precursors and
tetraethoxysilane (TEOS) [119] (Scheme 15).
2.2.5. Switchable-polarity solvents (SPS)
These solvents can be described as neutral liquids that can be
reversibly converted to polar ionic liquids when exposed to CO2
(Scheme 16). This conversion is reversible. The viscous ionic liquid
can be converted back to neutral liquids in presence of N2 or argon
gas or heat. By a judicious choice of the liquid amine, ionic liquid
carbamate salts can be formed. Secondary amines have been
recently described. These solvents have been described as a postreaction separation of the product from a homogeneous catalyst.
The example describes the polymerization of cyclohexene with
CO2 catalysed with Cr(salen)Cl without solvent. At the end of the
reaction, the polymer and the catalyst are dissolved in the NHEtBu
amine. By bubbling CO2 the amine is converted into the polar
carbamate salt in which the polymer precipitates. The catalyst
remains mainly in the solution [120122]. The limitation of these
solvents is the reactivity of the base. This class of ILs is further
developed in Section 5.3 of the review.
Scheme 16. Switchable Polarity Solvents (SPS).
2.2.6.2. Deep eutectic solvents (DES). Recently, some deep eutectic

mixtures with properties similar to those of ILs, have been
described. These mixtures can simply be obtained by mechanically
mixing two different components with no emission and mass
efciency (Table 2).
2.2.6.3. Metal salts anions. Many ionic liquids based on metal ions
have been developed [40,129]. Work has been rst focused on
chloroaluminates associated with imidazolium or pyridinium
cations. A variety of different anions are formed in solution
([AlCl4], [Al2Cl7], [Al3Cl10]) the ratio of which vary with
changing aluminium chloride composition. These ideas have
more recently been extended to other chlorometalate salts. The
resultant molten salts have the advantage that they are not water
sensitive, although they are in general, more viscous than their
aluminium analogues: to name just a few examples, [FeCl4],
[CuX3], [InCl4], [AuCl4], [CoCl4]2, [NiCl4]2, [PdCl4]2,
[Co(CO)4]. Ionic liquids with Cr or Mo based anions (Cr(O)3Cl)
or Mo(O)2(NCS)4 have been applied as self-supported catalyst for
oxidation, as well as polytungstate imidazolium complexes. The
lanthanide based [BMI]3[Ln(NCN)6(H2O)2] compound proved to
be low melting (Ln = lanthanide). These examples are scarce and
still quite exotic. In catalysis, these metal salts have mainly been
used as potential Lewis acids. Polynuclear anions have been
described in some cases such as [Zn2Cl5] [130], [Zn3Cl7];
[Fe2Cl7]; [Sb2F11], [Sn2Cl5]. These complex anions can be Lewis
acids strong enough and not air and moisture sensitive (the cation
can be based on choline cation). The soft indates based ILs have
exhibited interesting Lewis acid properties for Friedel-Craft
acylations and chlorozincates for Diels-Alder reactions or alkylation reactions [131,132].
The liquid version of the Monsanto catalyst for MeOH
carbonylation can be cited: [BMI][RhI2(CO)2] obtained by reaction
of [BMI][I] with [Rh2I2(CO)4] [133]. The introduction of the metal
ions inside the ILs is an interesting way to immobilize catalysts
while taking part of the potential ordered structure of the ILs.
Although less studied, these metals containing ILs could be used for
the preparation of nanomaterials. Several liquids based on
ferrocenated imidazolium have been reported [134]. Their main
applications are found in the domain of electrochemistry [135]. A
review on ILs crystals is also available [136].
12
Table 2
Examples of deep eutectic solvents.
Compound 1
Compound 2
Carboxylic acids
Li+ NTf2
Acetamide
Li+ NTf2
2.3. Latest advances in the preparation and purication of ILs

2.3.1. The different ways of ILs preparations
Different routes for the synthesis of ILs are described, each of
them presenting advantages and drawbacks. They can be
summarised as follows (Scheme 18):
(1) Metathetic exchange of anion (path A): This is probably the most
used pathway for the synthesis of ILs. The production of
alkylimidazole is industrial. The metathetic exchange of anions
often produces halide by-products (MX) which may be difcult
to eliminate by ltration especially for hydrophilic ILs.
(2) Neutralisation of base with Brnsted acids (path B) or direct
alkylation of alkylimidazole (path C): This route is interesting
because it avoids the presence of halide (atom efciency).
However, in the case of the direct reaction of Brnsted acid
(HX), it may be difcult to obtain ILs with high purity. Traces of
alkylimidazole or acid may be present in the nal ILs. The
alkylation reaction is limited to the reactivity and availability of
the alkylating agents. This method has been described for the
preparation of sulfate, phosphate or sulfonate based ILs.
(3) The carbonate route (path D): The use of dimethylcarbonate
(DMC) as a clean methylating agent to replace alkyl halides has
proved to be a new interesting route to avoid the presence of
halide and other by-products [137]. However this method is
Selected characteristics
Ref
Eutectic for 3:7 molar ratio

Eutectic point at 56 8C
Viscosity: 22.5 cP at 60 8C
Conductivity: up to 5.2 102 S cm1
Electrochemical window: about 3 V
[124]

Eutectic point at 12 8C, which is lower than choline chloride
(Mp = 302 8C) and urea (Mp = 133 8C)
[125]
Dependent upon the number of acid functionalities
[79]
Eutectic for 4.8:1 molar ratio

Eutectic points at 37.6 8C
Conductivity of urea/LiNTf2(3.6:1) is 2.3 104 S/cm at 25 8C
[126]
Eutectic for 4:1molar ratio

Eutectic points at 67 8C
The acetamide/LiNTf2 is a liquid at room temperature
between the molar ratio of 2:1 and 6:1
[127]

Liquid at 50 8C
Viscosity: 69.2 cP
Conductivity: 5.3 S cm1
[128]
limited by the availability of the acid (HX) or [NH4]+ salts. These

ILs have been produced on an industrial scale by Proionics/
BASF (Proionics is a PME specialised in the synthesis of ILs from
carbonate intermediates).
Synthesis of ILs using non conventional activation method
(microwaves or ultrasounds) has also been described [138].
However, ILs can decompose under sono-chemical conditions
[139]. Recently [BMI][BF4] has been synthesised with a yield of 87%
by a rapid one-pot solvent-free synthesis in a batch-mode reactor
using a microwave irradiation (frequency of 5.8 GHz) [140]. A new
environmentally benign process for the production of [EMI][OH] in
solution has been reported by an electrodialysis set-up [141]. This
process could be used for the purication of spent ILs. It is worth
emphasising here that N,N-dialkylimidazolium hydroxide ILs are
not stable as pure compounds or when they are concentrated in
aqueous solution. Formation of N-heterocyclic carbenes may
occur. They have to be kept in diluted solutions. A direct access
to anion-functionalised ILs consists in the one-step ring-opening
reaction of sultones (Scheme 19). The reaction leads to the
formation of zwitterions which have in general high melting points
(e.g. R1 = Bu, R2 = H, mp = 158 8C). These zwitterions can then react
with acids or LiNTf2 to generate new functionalised ILs [99].
Interestingly, this mixture is liquid at room-temperature although
very viscous. It is also ion conductive. The reaction of sultones has
been extended to the reaction of the nucleophilic chloride anion of
13
Scheme 18. General route for ILs synthesis: (path A) metathetic exchange of anion, (path B) neutralisation of base with Brnsted acids, (path C) direct alkylation of
alkylimidazole, (path D) the carbonate method.
Scheme 19. Direct access to functionalised ILs.
an ionic liquid. However the stability of these ILs remains limited at

temperatures lower than 150 8C [142].
2.3.2. Purication of ILs and analysis of trace impurities
It has very often been demonstrated that the physical and
chemical properties of ILs and their catalytic activity can be
signicantly inuenced by the presence of small amounts of
impurities. The quality of ILs has become an important
consideration and purications methods have been developed.
Typical impurities come from the incomplete synthesis of ILs. They
can be volatiles, alkylating agents, inorganic halides, protic
impurities, organic amines, water. Few purication procedures
are proposed in the literature. Recently, melt-crystallisation has
been described for ultra-purication of ILs and sample of 10 kg
capacity of [EMI][Cl] have been produced [143]. Decolourization of
ILs has been reported using activated charcoal [144], or by treating
the ILs with silica [145] or alumina [146]. However, it is also worth
mentioning the possible contamination of ILs when treated with
solid sorbents [147,148]. Acid impurities can be difcult to remove
from hydrophilic ILs as water washing is not possible. Acid
neutralisations by a column were reported [149]. Analysis and
traces analysis of impurities are still challenging and are eld of
fundamental research. A number of analytical protocols with their
limits of detection (when available) have been compiled [150].

Using the 1H NMR chemical shift of water taken as an NMR
impurity indicator, 1H NMR appears as a highly sensitive analytical
method for detecting Brnsted acid impurities [151]. Very low
concentrations of halide (<20 ppm and down to 5 ppm), not
currently measurable by ion chromatography, have been quantied in a wide range of ILs, using a special automated microuidic
device designed for electrochemical studies [152].
As a recent another example, X-ray photoelectron spectroscopy
(AR-XPS) has been proposed as a suitable method to determine
impurities down to an extremely low level if those impurities show
at least some surface activity in the IL system [153,154].
3. Structure and self-organisation of ILs at the supramolecular
level
3.1. Solvent properties and solvent effect
A solvent is generally characterized by macroscopic physical
constants (bulk properties) such as vapour pressure, boiling
point, density, cohesive pressure, relative permittivity er (dielectric constants), surface tension, refractive index. A large number
of studies have been devoted to the characterization of ILs bulk
14
Scheme 20. Schematic representation of the different type of interactions present in imidazolium-based ILs.
physico-chemical properties such as viscosity, density, surface

tension. These data are available in reviews and databases and will
not be reported and discussed here in detail [48].
It is just worth emphasising here that the convenient method
for determining dielectric constants fails in ILs because of their
high electrical conductivity. However, it could be measured for a
series of imidazolium-based ILs using microwave dielectric
spectroscopy. ILs can be classied as moderately polar solvents.
Dielectric constant e values are found in the range of 8.815.2,
decreasing with increasing the length of the alkyl chain on the
imidazolium cation, it varies little compared to the wide range of
values covered by molecular solvents [155157]. The dielectric
constants were found to depend mainly on the nature of the ILs
anions with the following trend [OTf] > [BF4] [PF6]. However, the abundant different interactions acting together in ILs
make them very complex (Scheme 20), so that it is not surprising
that a single physical parameter such as the dielectric constant is
incapable of adequately modelling the solventsolute interactions.
This parameter has often failed in correlating solvents effects
qualitatively and quantitatively. An example is given by the
solvent effect study on nucleophilic reactions in ILs compared to
molecular solvents [158] where Hugues-Ingold viewpoint using
dielectric constant as a measure of solvent polarity, proved to be
inadequate to describe the IL system. Nevertheless, for a rational
design and a better choice of ILs, better understanding of their
properties is required.
If we focus on conventional solvents, they are also characterized

by molecular-microscopic properties such as dipolarity/polarizability expressed as the Kamlet-Taft parameter (p*), polarity, Hbond donating acidity (HBD or Kamlet-Taft a parameter), H-bond
accepting basicity (HBA or Kamlet-Taft b parameter), electron pair
donor or acceptor forces, to name just a few. Solvatochromic
betaine such as zwitterionic betaine dye 2,6-diphenyl-4-(2,4,6triphenylpyridinium-1-yl)phenolate, called standard betaine dye
(N0 30), or Reichardts dye, has been used to establish UV/vis
spectroscopically a comprehensive set of empirical parameters of
solvent polarity, called the ET(30) or ETN scale [159,160]. This is
probably the scale that has been applied to the greatest number of
ILs [58,161]. For the same IL, different signicant values of ET(30)
reported in literature can be found. Several reasons are responsible
for these deviations, comprising the use of different solvatochromic probes. One of them is the presence of impurities in ILs,
especially water, that can considerably alter the ET(30) values and
change the polarity of ILs. The ET(30) values for about 80 ILs have
been reported. This work reveals that ionic liquids behave not as
superpolar solvents. The ET(30) values range ts quite well into the
existing empirical solvent polarity scale for molecular solvents. It
has also been found that the polarity decreases with increasing
temperature, while it increases with increasing pressure. The
ET(30) values of ILs are mainly controlled by the ability of the IL to
act as a hydrogen bond donor (cation effect) moderated by its
hydrogen bond acceptor ability (anion effect). The phenoxide
Fig. 4. Normalised solvent polarity scale (ET(30) = 0.00 for Me4Si and ET(30) = 1.00 for H2O)reproduced by permission of The Royal Society of Chemistry [58].
oxygen of the betaine, which is anionic, acts as a good hydrogen

bond acceptor. The result is a consequence of the existence of a
competition between the IL anion and the Reichardts dye solute
for the proton. The Reichardts dye scale thus emphasises the role
of the IL cations (Fig. 4). For example, ILs containing the 1,3dialkylimidazolium cation can be divided into those containing a
C(2)-H, which display a higher ET(30), and those substituted on the
C(2) which act as weaker H-bond donors and then are less polar.
This indicates that H-bonding occurs mainly through this C(2)-H
group.
The parameter of Kamlet, Abboud and Taft (KAF parameter: p*,
a and b) and the Gutmann donor number (DN), all three
determined UV/vis spectroscopically by means of carefully
selected solvatochromic reference compounds, could be benecial
to better understand the ILs solvent strength and treating the
multiple interacting solvent effects. These values have been
reported in different papers for ILs [162] and for ILs/organic cosolvents mixtures [163] and more recently for a series of [BMI]+
based ILs with different anions [149]. The authors found an
excellent correlation between the a (measured values) and the b
(values independently measured): the value of a signicantly
decreases with increasing the H-bond accepting strength of the IL
anion. Correlation of the 1H chemical shift of the proton in 2position of the imidazolium ring with the a value has also been
established.
3.2. Structure and organisation
Coulombic interactions are the dominant interactions between
the ions. But a simplied picture of ILs just considering
electrostatic interactions, as can be the case in molten salt (such
as in NaCl), would be very restrictive and not adequate to explain
some experimental results. Molecular interactions such as Hbonding, pp stacking and other dispersive forces such as van der
Waals interactions are also present. As an indication of the strength
of the different energies: the energy of H-bonds are generally
around 40 kJ/mol (for water), the van der Waals forces around
40 kJ/mol (for n-pentane), whereas coulombic interactions (ion/
ion) in ILs can be up to 600 kJ/mol.
The relationship between the crystal and the liquid structure of
representative ILs have been reported [164]. A wide range of
experimental techniques have been used to investigate the liquid
structure of ILs (Neutron Diffraction, X-Ray scattering, EXAFS,
NMR. just to name a few). A close correlation between the solid
structure and the liquid structure may be found. Probable locations
of the anion (such as Cl) around the imidazolium cation have been
proposed with a higher probability for the position closer to the
C(2) of the imidazolium ring (Cl is a good H-bond acceptor).
Larger anions such as [PF6] or [NTf2] are preferably located over
the centre of the imidazolium ring with in the case of [NTf2]
increased delocalization of the charge in the anion and softer ionic
bonding (Scheme 21). The chloride anion effectively has a highly
charged density, it is symmetrical, and forms a more regular
network than [NTf2] which is highly disordered and can display
different conformations with possible small cluster formation.
[MMI][PF6] shows quite strong ordering in the liquid phase as
found for the chloride based IL, despite the difference in H-bonding
ability of these two ILs.
However, H-bonding between imidazolium cations and anions
is still the subject of controversial debates. It is widely agreed that
this H-bond depend on the nature of the anions. The existence of Hbond can be crucial for understanding the solvation of transition
states in chemical reactions (competition for the ions between the
added species and the counter-ion). One may think it is possible to
control the solvation capability of ILs by changing the nature of the
anion [165]. The case of C(2)-alkyl imidazolium ILs is an interesting
15
Scheme 21. Possible location of the anions (represented as dotted circles) with
respect of the [RMI] imidazolium cation.
example [166]. The [BMI] cation forms stronger H-bonds than the
phosphonium cation with [Cl] as demonstrated by the exotherm
of mixing imidazolium and phosphonium ILs [167].
The strength of anioncation interaction inside the ILs
([RMI]+ + [A] $ [RMI][A]) has been investigated by ESI-MS (by
the abundance of fragments originating from C A C, with cation
named C and anion named A). Two classes of ILs have been
proposed: those with tightly associated anion to the 1,3-dialkylimidazolium cation such as: [CF3COO], [Br], [N(CN)2] and [BF4]
and those in which the anion is loosely interacting with the
imidazolium cation such as [OTf], [PF6], [NTf2]. Among the ILs
investigated, [NTf2] is the least interacting [168]. The weak [BMI]+
and [NTf2] interaction may have an important impact on metal
solvation. 1,3-Dialkylimidazolium [NTf2] ILs may be the solvents of
choice in catalytic systems that involve a chloride dissociation step
while being less solvating than water. For example, the ionic
strength of interaction has also been estimated by ab initio
calculation of the dissociative energies of different [BMI]+ or
[EMI]+ anion ion-pairs. For the [BMI]+ cation, it decreases in the
order [Cl] > [BF4] > [NTf2]. For the [EMI]+ cation, the intermolecular interaction energies of nine ion-pairs were studied.
The calculated interaction energies follow the trend
[CF3CO2] > [BF4] > [CF3SO3] > [NTf2] [PF6] (energies lie
between 78.4 and 89.8 kcal/mol) and the ectrostatic interaction
is mainly responsible of the attraction. For the [BF4] anion, the
interaction energies with pyrrolidinium or ammonium cation is not
signicantly different, demonstrating that the hydrogen bond with
C(2) of the imidazolium cation is not essential for the attraction.
Comparison with experimental ion conductivities show that the
magnitude and directionality of the interaction energy between ions
play also a crucial role in the dissociation and association dynamics
in ILs [49,169]. We have seen that for ILs containing the [EMI]+
cation, one of the strongest interactions is the CH anion
interaction via the proton in position 2. An interesting simple
way to determine the strength of this interaction is by 1H NMR
measurements. To exclude disturbing inuences on the ionion
interactions, all measurements must be carried out in neat ILs, in the
absence of other deuterated solvents. The 1H and 13C NMR shifts
obtained in that way show a good correlation with the calculated
ion-pair stabilisation energies (Fig. 5).
It has been shown that the presence of a co-solvent can
change the ion-pair strength. PGSE (Pulsed-Gradient Spin-Echo)
diffusion and HOESY NMR techniques have been applied for
studying inter-ionic interactions in ILs. For neat ILs such as
[BMI][BF4] and [BMI][NTf2], the diffusion constants, D-coefcient
values, are quite similar for the anion and the cation of the same
IL, and relatively small, but different for [BF4] and [NTf2] ILs.
Addition of methanol, as a co-solvent, results in an increase of the
D-values (also due to decreasing viscosity) up to a maximum
which may correspond to the completely solvated salt. The
methanol tends to separate the ions. On the contrary, in
dichloromethane, the anions and cations show strong HOESY
contacts which suggests that the cation and the anion form
strong ion-pairs in this solvent [171].
16
Fig. 5. Correlation between calculated ion-pair stabilisation energies and NMR-shifts for the proton and carbon at the C-2 position (reprinted with permission from [170].
Copyright 2009, American Chemical Society).
Scheme 22. Enantioselective hydrogenation of N-(30 -oxobutyl)-N-methylimidazolium (R)-camphorsulfonate. Effect of ion-pair interactions in the IL.
The most surprising effect of ion-pairing is probably demonstrated by the transfer of chirality in Michael type reaction
(Scheme 22). The hydrogenation of N-(30 -oxobutyl)-N-methylimidazolium (R)-camphorsulfonate using heterogeneous Ru on
charcoal in ethanol at 60 8C and 60 bar of hydrogen gives the
hydroxybutyl derivative with quantitative yield and enantioselectivities up to 80% ee. The correlation between the imidazolium
concentration and the enantioselectivity highlights the importance of ion-pair interactions. This chirality transfer approach can
be interesting, taking into account the large possibilities of
attaching substrates on imidazolium cations [172].
3.3. Toward a mesoscopic organisation
An understanding of the nano-structural organisation and
inter-ionic interactions of ILs is also crucial to understand their
solvent effect. The interaction of ILs with reactants, products,
activated molecules or complexes is another important concern
that needs to be taken into account to understand the solvent effect
on the outcome of the reaction. Different experimental and
theoretical methods have been reported to try to describe these
interactions. Three-dimensional supramolecular polymeric networks of cations and anions connected by H-bonds have been
several times evidenced (X-ray diffraction, NMR, neutron diffraction) (Scheme 23) [173,174]. The ability of ILs to give supramolecules has also been suggested by gas phase mass spectroscopy
experiments.
It is now proposed that ILs present supramolecular structural
organisation. Experimental and theoretical methods tend to
evidence the presence of aggregates in ILs. It is then difcult to

transfer the models developed for molecular solvents that are
described as a continuum with the properties of a macroscopic
phase. For example, the sole presence of interionic interactions in
ILs is not sufcient to explain all the features of Optical
Heterodyne-Detected-Raman Induced Kerr Effect Spectroscopy
(OHD-RIKES OHD-RIKES) [175]. Spectra show that these interactions may be responsible for a nanostructural organisation with a
three-dimensional ionic network and the presence of clusters of
alkyl chain into non-polar domains. A consequence of this
organisation is the existence of inhomogeneities in densities of
ILs evidenced by temperature dependence of Optical Kerr Effect
(OKE) spectra as a function of the size of the anions. NOESY NMR
[176] demonstrates the existence of inter and intramolecular
contacts in the case of [BMI][BF4], while only intramolecular
contacts are observed in the case of [NTf2] ILs. NOESY experiments evidenced cationcation interactions either as p-stacking or
as perpendicular T-shape assembly. These interactions could be
responsible for the aggregations. The size of these aggregates has
been measured by Raman Scattering signals as being in the range
of 10100 nm. These aggregates increase with the alkyl chain
length of the cation. X-ray diffraction [177] conrms the existence
of organisation and heterogeneities in neat and supercooled ILs.
Padua et al. developed molecular force eld [178,179] for the
molecular simulation of ILs based on 1,3-dialkylimidazolium
cations and extended to trialkylimidazolium and alkoxycarbonyl
imidazolium cations [180]. Molecular simulations show evidence
of the aggregation of side alkyl chain of the cations in non-polar
domains [181]. This conrms the presence of hydrophilic domains
Scheme 23. Representative scheme of extended three-dimensional network of Hbonds in [EMI][Cl] ionic liquid.
that are formed by the head groups of cations and anions and nonpolar domains that are formed by alkyl chains on the imidazolium
cations. It can be seen as if the liquid structure of IL has large
cavities. The behaviour of ILs in viscosity, diffusion coefcient, and
ionic conductivity, can now be attributed to the presence of
microdomains, specially the break in the trends observed for
alkylmethylimidazolium cation having alkyl chain longer than
butyl [182]. The heterogeneity of the ILs can also explain their dual
behaviour when they are used as stationary phases for gas
chromatography (they can separate polar and as well as non polar
alkane compounds) [183]. The question now is: could the structure
of ILs affect catalytic reactions? should channels favour diffusion of
small molecules? This will be discussed in section 4. But, there is
still few data available in the literature.
3.4. Solute-ILs interactions: what impact on organic reactions?
Many studies have focused on the cationanion interactions
(solventsolvent interactions) rather than ionssolute interactions
(solventsolute interactions or solvent solvation). In conventional
medium, solventsolute interactions are generally predominant
while in ILs, interactions inside the solvent can become more
important. The Diels-Alder reaction is an interesting example
because it is a key step in many syntheses used to prepare cyclic
structures, and because the reaction performances in term reaction
rate and selectivity have been widely studied and are highly
solvent dependent. In the case of the reaction of cyclopentadiene
17
and methyl acrylate, the ability of the IL to act as H-bond donor

(cation effect) appeared to be a key criteria to explain the
enhancement of reaction rate and endo-selectivity [184]. This
effect has to be moderated by the H-bond acceptor ability of the IL
(anion effect). ILs with strong H-bond interaction between the
cation and the anion (contact pair-ions) are poor solvents for DielsAlder due to competition between the anion and the H-bond
acceptor dienophile for H-bonding with the cation. It is not
surprising that low yields have been reported for dialkylimidazolium bromide and triuoroacetate ionic liquids [185]. This Hbonding with the substrate can be inuenced by p-stacking of the
imidazolium cations and H-bonding interactions between the
cation and the anion of the IL. It can be manifested either with the
IR with the C(imidazolium)-H A stretch which is around
3126 cm1 for [BMI][PF6] and 3060 cm1 for [EMI][Cl] or by the
1
H NMR shift of the C(2)-H proton of the imidazolium. The highest
endo:exo selectivity for cyclopendiene/methylacrylate reaction is
obtained for the [NTf2] series which displays the least strong Hbonding interaction between the cation and the anion. When the
cation is functionalised with H-bond donor (e.g. hydroxy group),
even better selectivity can be reached [186]. The rationalization of
the solvent effect in the Diels-Alder reaction of cyclopentadiene
with three different dienophiles (acrolein, methyl acrylate and
acrylonitrile) has been reported using multiparameter linear
solvation energy relationships (LSER). This work provides evidence
that the reaction performances (reactivity and selectivity) are
dependent on the solvent but also upon the nature of the
dienophile. In the case of acrylonitrile, a non-carbonyl containing
dienophile, the effects on selectivity are mainly inuenced by the
hydrogen bond acceptor ability of the solvent and other factors
than the hydrogen bond donor ability of the solvent as it is the case
in the carbonyl-containing dienophiles [187].
The nucleophilic substitution reactions provide another good
example of model reaction to examine the IL effect. In molecular
solvents, the Hughes-Ingold qualitative model describes the solvent
effect considering the pure electrostatic interactions between ions
or dipolar molecules in initial and transition state (solvent polarity).
This model does not take into account the H-bonds interactions and
proved to be limited to describe ILs effect. Kamlet-Taft linear
solvation energy relationship has also been utilised to describe ILs
effect on nucleophilic reactions. The characteristic values of a, b, and
p* have been collected for ILs [165]. The solvents hydrogen donor
ability (a value) appears as the dominant effect in reducing the
nucleophilicity of the nucleophile and slowing the reaction rate (e.g.
reaction of amines with methyl-p-nitrobenzenesulfonate) [188].
Hard and soft natures of the nucleophile proved to be also important,
the [BMI]+ cation of the ILs acting as a hard solvent in interacting
more strongly with hard anions (e.g. [Cl]) than soft ones (e.g [CN]).
For example, the nucleophilicity of halide anions (e.g. [Br]) in the
SN2 reactions of methyl-p-nitrobenzenesulfonate (Scheme 24) was
rather reduced in ILs relative to molecular solvents (the reaction is
15 times slower in [BMP][NTf2] than in dichloromethane, and it is
roughly 2 times slower in [BMI][NTf2] than in [BMP][NTf2]). This can
be ascribed to the existence of strong H-bond between the
nucleophile (the anion, particularly the chloride) and the [BMI]+
cation. This difference arises largely from the a value (Table 3).
Another systematic study on nucleophilicity of a series of anions on
the substitution reaction of methanesulfonic group was conducted
in different ILs and compared with that obtained in organic solvents
Scheme 24. Nucleophilic SN2 substitution reactions.
18
Table 3
Quantitative kinetic studies of nucleophilic SN2 substitution reactions of [Br] with
methyl p-nitrobenzenesulfonate [188].
[BMI][NTf2]
[BMP][NTf2]
CH2Cl2
k (M1 s1)
p*
0.0195
0.0296
0.460
0.617
0.427
0.042
0.243
0.252
0.014
0.984
0.954
0.791
(PhCl, DMSO and MeOH). The results emphasise the predominant

role of water for hydrophilic anions ([Cl], [PhCO2]). In this case, the
interaction of the anion with the imidazolium has a lower effect.
These results conrm that water molecules creates H-bond with the
imidazolium cation replacing the cationanion interactions present
in the ILs [189]. Higher reactivity is also observed in C(2)-protected
imidazolium-based ILs.
The case of charged electrophiles within the framework of SN2
reactions is also of fundamental interest since many catalytic
centres carry positive charges. The effect of b (H-bond accepting
ability) is dominant: low b values lead to acceleration of reaction
rate. This is the case for less basic [NTf2] based ILs. However, no
unexpected special effect of ILs was observed [158].
The reaction of chloride ion with an ionic electrophile
(sulfonium associated with [NTf2] or [OTf]) was studied in
several molecular solvents and ionic liquids (Scheme 25). The
nucleophilic substitution reaction does not take place in either
strong dissociating molecular water solvents or in methanol. In
non-dissociating solvent, the reaction is supposed to occur via a
solvated ion pairs. The behaviour of this reaction in ILs is
different from that in molecular solvents, the kinetic experiments in ILs are in favour of reaction via dissociated ions. The
authors conclude that ILs can be considered as super-dissociating solvents, this effect arising from the fact that ILs are at the
same time liquid and ionic. The reaction mechanism would
proceed through a true SN2 reaction of free solvated ions rather
than with a ion-pair mechanism seen in molecular solvents
[190].
In the case of the esterication reaction of methoxyacetic acid
with benzyl alcohol in ILs, it appears that the IL basicity,
characterized by the b value, is the dominant parameter in the
LSER, and determines the reaction rate. The best rates are obtained
in low basicity solvents. In other words, a high b value corresponds
to a high proton afnity and thereby low proton availability to a
low reaction rate, as observed. The IL plays the role of levelling of
protic acids [191].
With these model reactions, we can see that the interactions
between ILs and different species can occur in diverse and complex
ways and can signicantly modify their reactivity. In the chapter
below, we will discuss in more detail the type of interactions of ILs
with selected solutes such as water and aromatic hydrocarbons.
3.4.1. Interaction with water
The role of water (or other substrates) in modifying IL properties
has been a central focus of interest these last years [41,182,192]. But
this is still controversial. The IL effect has been illustrated by the
examination of water solvation at low and high concentrations. At
low concentrations, spectroscopic measurements such as IR [193]

and dielectric constant [194] provide evidence that water is
molecularly dispersed in 1-alkyl-3-methyl imidazolium-based ILs
([H2O < 2 M]. When the water concentration is increased, small
water aggregates form which lead to the formation of a well-dened
water hydrogen-bonds network [194,195]. The detailed nature of
water interactions with highly diluted in 1-alkyl-3-methyl imidazolium-based ILs with [BF4] and [PF6] anions has recently been
investigated combining vibrational spectroscopy based on IR
absorption, Raman scattering and DFT calculations [196]. It is found
that the local organisation between ions precludes any specic
interactions between water and the proton of the imidazolium
cation. Water would be doubly hydrogen-bonded with two anions,
in symmetric 2:1 [Anion HOH Anion] structures.
PCl3 and POCl3 show unexpectedly high hydrolytic stability in
wet ILs. For example, in the [NTf2] based ILs, PCl3 was soluble at
concentrations up to 0.20 M and in [BMP][NTf2] was found to be
hydrolytically stable for weeks, even when stirred in air and
without drying the IL. The ability of even wet ILs to stabilise
hydrolytically unstable solutes may be understood by considering
the interaction of water in the IL. The nucleophilicity of water, and
therefore its hydrolysis activity, can be reduced due to its
interaction with IL anions. In hydrophilic ILs, the higher water
content results in higher rate of hydrolysis [197]. Similar
stabilisation of reagents with respect to hydrolysis has also been
described in catalytic reactions in ILs [198,199].
Interestingly, ILs have been used to improve the solubility of
hydrophobic compounds in water. For example, the solubility of
acetophenone in aqueous solution can be increased by a factor of
10 by addition of [BMI][BF4] (the same effect is observed for
[MMI][MeSO4], which can be important for application in biocatalysis, for example. This phenomenon can be explained by the
ability of ILs to form small aggregates which are solvent
dependent. ILs can behave as hydrotropes [200].
3.4.2. Interaction with aromatic hydrocarbon. Clathrate behaviour
Aromatic hydrocarbons show unusual high solubility in ILs in
comparison to aliphatic compounds. This solubility decreases with
an increase of the molecular weight of the hydrocarbon but the
differences of solubilities of o-, m- and p-xylenes are not signicant.
It has been reported that imidazolium-based ILs can form liquid
clathrates in presence of aromatic hydrocarbons [201]. Dialkylimidazolium cations are able to form specic and oriented interactions
with arenes (and chloroalkanes). For example, in the salt crystal
[BMI][PF6], 0.5 benzene, a three-dimensional network has been
observed with H-bonds between anion and cation. This results in the
formation of channels containing the benzene molecules. Short
interactions between methyl hydrogen of the cation and aromatic
hydrogen are present [202]. Interactions between p-aromatic
systems and inorganic cations (Li+, Na+, K+, or Ag+) or organic
cations (ammonium) are already well-known as the p-cation
interaction, important in biochemistry, and experimentally evidenced [203]. A detailed study conducted by NMR (ROESY
experiments) and by molecular simulation shows difference of
interaction of toluene with the ILs as a function of the substitution of
the C(2) of the imidazolium cation. In the case of the [BMI] cation,
Scheme 25. Reaction of chloride ions with ionic sulfonium electrophile (A = NTf2 or TfO).
toluene is located closer to the methyl group at the end of the butyl
chain, whereas in the case of [BMMI]+ cation, toluene was closer to
C(2)-Me of the imidazolium. The H-bonding association between
[BMI]+ and the [NTf2] is too strong to be cleaved by toluene. In the
case of C(2)-Me cation, the less strongly bonded IL network renders
possible the penetration and interaction of toluene [204].
3.4.3. Interaction with chiral substrates: induction of chirality?
Some Chiral ILs have been designed and synthesised, they have
already been applied in different elds such as asymmetric synthesis
(see reviews), stereoselective polymerization, chiral chromatography, liquid crystals, chiral resolution and as NMR shift reagents.
Chiral solvents have been reported in asymmetric syntheses.
However, low enantioselectivities are most of time obtained. In
the Baylis-Hillman reaction of benzaldehyde and methyl acrylate in
presence of a base, chiral ILs (Scheme 26) demonstrate their ability in
the transfer of chirality, even if the enantiomeric excesses are still
moderate. The presence of an alcohol function on the N-alkyl-Nmethylephedrinium is primordial and acts as a xing point of the CIL
on the reactants. It is indeed assumed that the OH group is connected
with a carbonyl function of the substrate (from either benzaldehyde
or methyl acrylate) via H-bonding. However, with N-methylephedrine, very low ee are obtained which also shows that the
ammonium group plays a crucial role in the chirality induction.
Even if not directly demonstrated, it seems that the key of effective
asymmetric induction is the existence of both strong intermolecular
interactions, like electrostatic attraction and hydrogen bonding,
between ionic solvents and intermediates or transition states of the
diastereoselective reaction step. The need of H-bonding in the
transfer of chirality has also been conrmed in the case of borate
based CIL bearing maleic acid functions. In this latter case, by
incorporating the acidic centre into the chiral anion of the solvent,
the IL offers the possibility of establishing a bifunctional interaction,
which allows monofunctional achiral nucleophiles to be used as
catalysts [205].
3.4.4. Interaction with acid and base: toward new scale of acidobasicity
The interest of ILs as solvents to perform acidbase reactions
has been recently increasing. A simple way to generate and
modulate the acidity is to add a Brnsted acid into the ionic liquid.
In that case a new scale of acidity can be obtained either by varying
the acid concentration in the IL or by changing the nature of the
ionic liquid [206]. If quite a lot of acid-catalysed reactions have
been reported in ILs, very few studies have been devoted to the
quantication of the acidity level of the proton in these media.
Nevertheless, as the acidity of protons is mainly determined by
their solvation state, the properties of protons will depend strongly
on the nature of the IL and the nature and concentration of the acid.
A rst apparent relative estimation of the proton acidity level has
been reported using the determination of the Hammett acidity
functions, by UVvis spectroscopy [207]. For a similar content of
added strong acid, the anion of ILs plays a fundamental role; the
acidity levels are in the order: [PF6] > [BF4] > [NTf2] > [OTf]
thus implying that the solvating power (or basicity) of the anions
follows the reverse order. The presence of basic impurities in the
19
ILs can also have a dramatic effect. Even if absolute acidities cannot
be determined with this method, global acidity must be (much)
higher than that observed in water.
3.5. Molecular modelling
Because of the potential number of cationanion combinations,
experimental investigations of all ILs properties are very difcult,
quite impossible. A molecular-based understanding of their
properties is important for their rational use. If molecular
dynamics (MD) calculations have been developed for inorganic
melts, liquid salts based on organic ions were not so extensively
explored. ILs are indeed not simple uids. The unusual complexity
of intra and intermolecular interactions in ILs renders interpretations very difcult and gives rise to controversies speculations.
Computer simulations have played an important role in the
prediction of physico-chemical properties of ILs starting from the
molecular structure of ions. The structure-properties relationship,
called QSPR (Quantitative Structure-Property Relationship), drives
most of theoretical studies. Many properties, useful for catalytic
applications, have been predicted requiring a combination of
several theoretical models and approaches (IL melting point [208];
solubility and partition coefcient of organic solutes in ILs [209];
viscosity [210]; surface tension [211]; ionic conductivity [49].
Cationanion interactions can be obtained using quantum
chemical calculations in gas phase. This calculation gives details on
ion-pair stability, intramolecular geometry, and orientation of ions
in the pair and allows a better understanding of H-bonds and
charge transfer between ions. One limitation is the size of
dialkylimidazolium cations. Different correlations could be
obtained between the energy of ion pairs (ion-pair association
energy) and the different structure of ILs and their melting points
[212]. Based on DFT calculations, the high viscosity and the low
pressure of ILs could be rationalized with the location of the anion
and the possible H-bonds with the dialkylimidazolium cation. The
transport properties in the liquid are affected by the presence of
the anion which inuences the barrier for rotation of the alkyl (e.g
butyl) present on the imidazolium cation.
Ab initio techniques raise some issues: the poor performance of
DFT in dealing with systems bearing delocalized charge; the
problem associated with the calculation of a meaningful charge
on each atom in a delocalized molecular ion. Ab initio molecular
dynamics, which combines electronic structure calculations with
conventional MD (called AIMD), is the only technique able to predict
the intermolecular structure of ILs (under specic thermodynamic
conditions). However, a major limitation of such simulation is the
length and time scale that can reasonably be explored and the need
for extensive computational resources. Long range organisation of
ILs cannot easily be explored with this method. These studies have
essentially been performed on dialkylimidazolium associated with
halide or [PF6] anions. They clearly identify the existence of H-bond
between C(2)-H and the chloride anion [213]. The signicance of the
simulation crucially depends on the quality of molecular force eld
used. Different groups tried to develop and rene force elds for ILs
[214]. The growth of computational studies in ILs was driven by the
development of force elds for a wide variety of ILs [215]. The
Scheme 26. Baylis-Hillman in N-alkyl-N-methylephedrinium. First example of transfer of chirality. Because of the strong interactions between the IL and the reactants
enantiomeric excess have been obtained.
20
validation with experimental results (Raman spectroscopy) was

made in some cases. Force elds have been extended to other
cations than imidazolium such as pyridinium, tetraalkylammonium, guanidinium, tetraalkylphosphonium. Atomistic MD simulations with empirical force elds are used to describe liquid state
structure and dynamic properties of ILs. For example, the local
electrostatic interaction of benzene with [MMI][Cl] or [MMI][PF6]
IL was found to be one of the possible reasons for the higher
solubility of aromatic hydrocarbons in ILs [216]. The interaction of
CO2 and with [BMI][PF6] could also be studied [217]. Monte Carlo
simulations can be used to calculate solubility of gas, but this
method remains limited due to the complexity of ILs [218]. To
evaluate mass transfer in IL biphasic systems, molecular dynamics
have been developed to study the interface involved in systems
such as 1-hexene and ILs used in hydroformylation reactions
[219]. The number of published data on the solvent-ILs equilibria
is still limited although this information is of prime importance
when ILs are involved in reactions and separation processes. The
COSMO-RS thermodynamic model has been used to describe the
solvent-ILs systems. It has been able to evaluate the separation
ability of ILs for a given separation task such as ethanolwater or
hexenehexane separations [220].
An interesting properties of ILs is that they can exhibit
nanostructural organisation. This long-range ordering can be
ascribed to the presence of the (long) alkyl chain on the
imidazolium cation which can generate dominant van der Waals
interactions. Evidence of this ordering was found by different
groups and could be experimentally conrmed (X-ray scattering
experiments) [177]. Coarse grain models (CG models) have
tentatively been used but it remains challenging. All these methods
are computational time-consuming and need large experimental
databases. They are at the moment mainly developed on simple
ILs often taken as model such as [RMI][PF6] or [RMI][X] which are
not the ILs under study. It was recently found that the molecular
volume of ILs can be a useful and powerful tool to predict some
fundamental physical properties of ILs such as melting points or
dielectric constants. The molecular volume Vm of a salt has been
dened as the sum of the ionic volume of its constituents. When
not described, the molecular volume of ions can be calculated (by
quantum chemical calculations) with quite good accuracy.
Correlations with ILs viscosity, conductivity and density have
been established. This relationships are available only on pure ILs
[221]. The modelling of the reactivity of ILs has been examined by
DFT (and DFT/MM) calculation for a specic reaction (SN2
intramolecular rearrangement). The energy barrier has been
described in ILs and compared to that calculated in other
environments. A simple model is proposed to explain the solvent
effect [222].
In conclusion, we can consider ILs as a new class of solvents the
chemical properties of which can be rationalized with multiparameter linear solvation energy relationships and correlate with
their effect on chemical reactions. But this approach is not
sufcient. Imidazolium-based ILs display a pronounced selforganisation in the solid state as well as in the liquid phase and
then can also be regarded as liquid supports in which the
introduction of other molecules may occur with the formation of
inclusion-type compounds. We will try to illustrate below, with
selected examples, how ILs can behave differently than organic
conventional solvents.
4. How the ILs can affect the catalytic reactions pathway?
ILs proved to be very complex solvents. They can solvate polar
and non-polar species, they can behave as polar or non-polar
solvents. Besides their chemical characteristics, their physical
properties such as an elevated viscosity can affect the diffusion and
reduce reaction rates. The solubility of gas or the selective

solubilisation of reactants relative to the products can also change
the reaction selectivity. The formation of primary reaction
products can be favoured by their selective extraction from the
IL catalytic phase in an organic upper phase. It is then difcult to
rationalize the IL effects on chemical and catalytic reactions.
Nevertheless, it would be of primary importance to understand
how their physico-chemical properties can affect the outcome of
catalytic reactions in order to be able to choose the best ILs for a
given reaction. Solvation properties, interactions with solutes,
substrates, transition states, metal complexes, reactants, their
cohesive pressure, their degree of organisation and their viscosity
are all to be considered when ILs are used as solvents. To date, the
ILs effects have been best described and rationalized on chemical
reactions rather than on catalytic reactions involving transition
metal complexes. We will see below that some effects of ILs are not
expected and then not under control. In some cases, the generation
of the active catalyst has been dependent on the nature of the ILs.
ILs can inhibit or promote the formation of the active species. They
can also dramatically affect the outcome of reactions [223].
4.1. Some unexpected effects of ILs
4.1.1. Effect of ILs impurities
Water [224], halides, bases and metals are the most prevalent
impurities present in ILs. While water can be accumulated in ILs by
absorption of moisture (ILs are very hygroscopic), the other
impurities mainly come from ILs mode of preparation. The
impurities have been recognised as affecting both physical and
chemical ILs properties [225]. Most of time, they have a poisoning
effect on transition metal catalysed reactions. For example,
chloride anions present in [BMI][BF4] has been detected as a
cause of deactivation of the cluster [H4Ru4(h6-C6H6)][BF4]2 used as
pre-catalyst in the hydrogenation of arenes [226]. In the case of 1octene metathesis catalysed by ruthenium complexes (Grubbs or
Hoveyda type precursors), the purity of ILs proved to be very
important for the reproducibility of the results. An extensive study
shows that catalyst deactivation by impurities increases in the
order of water < halide < 1-methylimidazole, but no deactivation
mechanism is described [227]. This result again underlines the
importance of the characterization of the ILs and the identication
of possible impurities.
4.1.2. Effect of water and acidic protons
Many papers describe the use of protonated imidazolium
(Protic ionic liquids) as acid catalysts for organic synthesis. In these
systems it is often not clearly identied if the system is completely
anhydrous. It is worth noting that H(OTf)2 can be a stable acid
which may be formed in the presence of water. This acid has
already been described as stable [18,91]. Protic ILs based on alkyl
imidazolium cation have also been used as promotors (proton
reservoir) for proton and metal-assisted catalytic reactions such as
Pd or Rh catalysed dimerisation of methyl acrylate and Ru
catalysed ring closing metathesis N,N-diallyltosylamide. In both
cases, protons are known to enhance the reaction performances.
The use of protic ILs leads to signicant improvements both in
activity and selectivity. As the level of acidity of the NH proton of
the IL is very low, it is probable that the effect of the ILs is better due
to the presence of residual acid coming from the IL preparation.
The acidity level of the proton, even present at very low
concentration, can be exalted in the ILs [228].
Another interesting example of the effect of ILs is when chloride
dissociation from the transition metal is a key step in the
mechanism of activation. This is the case of the hydrogenation
reactions of arenes catalysed by ruthenium(II)-arene diphosphine
complexes in biphasic aqueous systems [229]. The enthalpy of
Scheme 27. Dissociation of the chloride anion in [BMI][Cl].
interaction of the chloride anion with the 1-butyl-3-methylimidazolium has been estimated by variable-temperature 1H NMR
measurements (Scheme 27).
In [BMI][OTf], the solvation enthalpy of the chloride
[DHsolv = 46.2 kJ/mol], is about eight times lower than the
solvation enthalpy of chloride in water. The strong coordination
ability of the chloride anion in 1-butyl-3-methylimidazolium ILs
can be related to the low solvation enthalpy of chloride in such
ionic liquids (the energy of interaction of the chloride with [BMI]+
is relatively weak: 15 kJ/mol). This can explain that chloride
dissociation from a transition-metal complex can be thermodynamically disfavoured in ionic liquids and might be inhibited in
these solvents. An example is given by the catalytic activity of
cationic ruthenium(II)-arene diphosphine complexes in different
ILs systems compared to water [230]. In ILs, without any water, the
Ru(II) precatalyst is inactive. Addition of water to the IL
([BMI][OTf]:H2O 50:50) results in activation of the Ru complex
and formation of an active hydride species (Scheme 28). This
example shows the crucial role that water can play in facilitating
the solvation of the dissociated chloride.
Now in neat and dried ILs, the activation of the ruthenium(II)
catalyst precursor occurs via an unexpected mechanism, which is
different from the activation mechanism that takes place as
previously described in water or in water-ILs for the same reaction
[231]. Both the cation and the anion of the IL display an important
effect (promotor or inhibitor) on the rate of styrene hydrogenation
which can be correlated with the differences in capability of the IL
to solvate chloride.
4.1.3. Effect of bases
A key step in the synthesis of most ILs is the alkylation of 1methylimidazole with the corresponding 1-haloalkane. ILs have
21
been described as solvents able to increase amine basicity with

respect to conventional solvents [232]. Residual unreacted Nmethylimidazole can remain in ILs and act as a base in promoting
some organic reactions [233]. For example, it has been observed
that bases such as L-proline or piperidine could be better basic
organo-catalysts for Michael additions in ILs than in dichloromethane [234].
The presence of impurities may play a signicant role on
nanoparticle stability in ILs. Water or halides are the most cited.
However, attention must also be paid to N-methylimidazole. In
recent work, it has been demonstrated that when gold nanoparticles were synthesised in base free [BMI][PF6] via reduction of
HAuCl4 with NaBH4, aggregation of Au particles was observed after
a short period of time. On the contrary, when 1-methylimidazole is
present, even at low concentration, particles are stabilised. PdAu
bimetallic nanoparticles stabilised in a similar way in IL have been
applied to the hydrogenation of allyl alcohols. This result can
explain the discrepancies in the literature concerning the stability
of nanoparticles. This also shows than highly pure ILs can in some
cases be detrimental [235]. The lack of basic entity in phosphonium based ILs, when associated with low nucleophilic anion such
as [NTf2], can prevent some base-mediated side reactions or
inhibition, but these ILs present other limitations such as their
viscosity and long alkyl chain on the cation [236].
4.1.4. ILs as additives: surprising effect!
This effect has been described for hydroformylation reaction of
ethyl vinyl acetate to yield ethyl lactate, the branched (noted b)
product is the desirable isomer (l = linear isomer). In ILs superior b/
l ratio can be obtained compared to the selectivity in toluene. This
increased selectivity is dependent on the level of IL in the reaction
medium, thus demonstrating a surprising effect of ILs. But more
surprisingly, this effect can be maintained when low level of ILs are
blended with an organic solvent which offers a good compromise
between rate enhancement and selectivity. The selectivity is
mainly driven by the electronic properties of the ligand. Phosphite
ligands give the best results in terms of activity and selectivity. This
effect of ILs is not really understood [237].
Another example of a nice effect of IL is given in the
enantioselective rhodium-catalysed hydrogenation of dimethyl
itaconate and methyl N-acetamido acrylate using Binap type
ligand in presence of chiral IL [238]. The combination of a racemic
ligand and a CIL either as reaction medium, or as additive gives
Scheme 28. Proposed mechanism of formation of the Ru active species for the hydrogenation of arene in water and in presence of ILs.
22
Scheme 29. Enantioselective Rh-Binap-catalysed hydrogenation.
Scheme 31. Example of [NTf2] coordination to Ti and Fe complexes through the O

and N atoms, respectively.
enantioselectivities identical to that obtained with enantiopure

ligand (Scheme 29). Even more, the association of CIL with the
enantiomerically pure ligand leads to enhanced enantioselectivities with an inverted absolute conguration in the product
compared to those obtained in organic solvents. Experiments
provide evidence that the key role of the CIL is as a chiral
poisoning in blocking the catalytic cycle for one of the two
enantiomers of the catalyst.
Ionic liquids have been recognised as promising solvents for
enzymatic reactions. Used as pure solvents they have been also
found to completely inhibit cellulase from Trichoderma reesei
[239], laccase C from Trametes sp. [240] or lipase from Candida
Antarctica [241,242]. However used as additives (small percentages of ILs in an organic solvent) can efciently improve
biocatalytic processes [243,244]. In a more recent paper, doping
the reaction mixture with 1-methylimidazole or [BMI][BF4] results
in both case in a notable improvement in lipase-catalysed
transesterication activity [245]. The effect of 1-methylimidazole
can be surprisingly compared to that of [BMI]+, but no rational
explication can be drawn.
nation, the mode of coordination depending on the softness of the

metal centre [248].
For example, the titanocene Cp2TiMe2 can be stabilised by
coordination to the [NTf2]. It coordinates to two [NTf2] anions
trough a monodentate metal-oxygen binding mode. Soft metal
centre are expected to prefer nitrogen coordination over oxygen.
This is the case of iron complex in Scheme 31. Surprisingly, the
reaction of YbI2 with the [PMP][NTf2] ionic liquid leads to the
formation and isolation of [PMP]2[Yb(NTf2)4]. This can maybe
sometimes explain why inorganic compounds are soluble in ILs
[249]. Metal complexes stabilised by the [NTf2] anion are
rendered signicantly more electrophilic compared to analogous
halide species.
[NTf2] can even be considered as nucleophilic anion when it is
found to be more reactive than [Br] in heterolytic dediazonation
reactions [250]. The coordinating ability of [NTf2] anion could also
explain the inhibiting effect observed in the oligomerisation of
ethylene catalysed by di-imine Ni(II) complexes activated with
MAO. When only one equivalent of [BMI][NTf2] relative to the
Ni(II) complex is added, activity drops down signicantly. With
addition of 10 equivalents, the system is nearly inactive,
demonstrating the poisoning effect of the ionic liquid on the Ni
catalyst. However, by using 10 equivalents of a very weakly
coordinating anion such as [B(3,5-(CF3)2C6H3)4] named [BArF]
anion, the activity is less decreased. It can be assumed that the
interaction of the [BArF] anion with the cationic nickel or with the
aluminium centre of the activator is weaker than with the [NTf2]
anion [251].
In chloroaluminates, Ni-catalysed olen oligomerisation is now
well understood. The inuence of the chloroaluminate composition on the overall mechanism of the catalysis has been established
using Raman spectroscopy. The resulting ionic liquids play the dual
role of solvents and nickel activator. The nature of the anions
present in the chloroaluminate IL inuences the activity of the
4.2. When ionic liquids are involved in the formation of metal

complexes
4.2.1. Complex formation involving anions
Most papers dealing with organometallic and ILs perceive ILs as
being chemically inert, assuming that the IL anions do not
coordinate with the metal. But when stronger ligands are absent,
even weak coordinating anions can complex to metals. Examples
are now reported in which the supposed non-coordinating anions,
such as [NTf2], bind indeed to the metal centre, even under mild
conditions [246,247]. In Scheme 30, different binding mode of
[NTf2] are proposed: monodentate nitrogen or oxygen coordination and/or bidentate oxygenoxygen or nitrogenoxygen coordi-
Scheme 30. Coordination modes of the [NTf2] to metal centre (M).
23
Scheme 32.
system. In presence of chloride anions, anionic Ni species are

formed which proved to be completely inactive in presence of
aluminium alkylating agents (Scheme 32). On the contrary, acidic
alkylchloroaluminates activate the Ni(II) precursor, the activity of
which being dependant on the composition of the IL (AlCl3 and
EtAlCl2 to [BMI][Cl] molar ratio) [252].
Formation of anionic [PdX4][BMI]2 metal complexes are also
described when PdCl2(COD) are put in [BMI][X] (X = Cl or Br).
Chloride anions inhibit the Pd activity for the methoxycarbonylation [253]. Wilkes reported that Cp2TiCl2 (Cp = cyclopentadienyl)
associated with EtxAlCl3x catalyses the polymerization of
ethylene in ([EMI][Cl]/AlCl3) acidic chloroaluminate (the molar
ratio of AlCl3 to imidazolium chloride is greater than 1) [254].
Analogous zirconium or hafnium complexes display no activity.
The lack of activity of Zr and Hf complexes may be ascribed to the
complexation of [AlCl4] anion to the metal centre resulting in a
strong MClAl bond precluding formation of the MR active
catalyst (Cp2MCl2 + [Al2Cl7] $ Cp2MCl(AlCl4) + [AlCl4]). The MCl bond strength was shown to increase according to the order TiCl < Zr-Cl < Hf-Cl. The coordination of [AlCl4] on titanium is weak
enough to allow its alkylation with the alkylaluminium derivative
and to form the suspected Cp2TiR(AlCl4) active species. This
example demonstrates the importance of the solvation properties
of the anion.
Research on ILs with non-halogenated and non-coordinating
anions continues to be a eld of investigation. New anions such as
[Al(ORf)4] (with Rf = peruoroalkyl group) are now proposed but
they lead to relatively high transition temperature and roomtemperature viscosity. However, it is interesting to note that the
salt [NBu4][Al(OC(H)(CF3)2)4] has a melting point of 42 8C but it
decomposes above 190 8C [255]. The salts [NBu4][B(C6F5)4] and
[NBu4][B(C6H3(CF3)2)4] have also been reported both to be very
stable [256,257].
complexes to form carbene-Pd that can be in some cases good

catalysts for Heck or Suzuki reactions [260]. The in situ formation
of mixed Pd phosphine/imidazolylidene Pd complexes has been
demonstrated, and these are active species. The formation of 1,3dialkyl-2-arylimidazolium salts has also been observed and these
salts can act as source of arene in the reaction. This shows that
both oxidative addition and reductive elimination of dialkyl-2arylimidazolium salts from and to the palladium can occur
[261,262].
In some other cases, the formation of such carbenes can have a
detrimental effect on the catalytic performances. An example is
the case of the telomerisation of butadiene catalysed by Pd(II)
complex associated with TPP (TPP/Pd = 3) with MeOH as the
telogen [263]. The reaction leads to the formation of the 2methoxy-octadiene isomers and to the butadiene dimers
(Scheme 33).
In this reaction, the catalyst cycle is thought to pass through a
low coordination Pd(0) intermediate, the general problem is the
separation of the catalyst and the formation of Pd black. In [BMI]+
or [EMI]+ based ILs, butadiene conversion is very low, surprisingly
there is no particle formation. It was established that the catalyst
deactivation was attributed to stoichiometric reaction between the
dialkylimidazolium salt and Pd. Addition of stoichiometric
amounts of [BMI][NTf2] proved to be enough to deactivate the
catalytic system. In N-butylpyridinium or dialkylimidazolium
substituted in position C(2), the activity of the system was
recovered. However in pyridinium salt, Pd black is formed and the
system rapidly deactivated. This deactivation can be attributed to
the decoordination of phosphine ligand from Pd to form a
phosphonium salt (Scheme 34).
The formation of metal-carbene can also occurs in situ by the
direct oxidative addition on electron rich Ni(0), Pd(0) or Pt(0)
complexes [251,264,265]. In the case of ethylene dimerization
4.2.2. Complex formation involving cations

A key of understanding of the properties of imidazolium salts is
the acidity of the C(2)-H. The presence of a base is not always
needed for the formation of the corresponding N-heterocyclic
carbenes [258]. It is worth noting that the protection of C(2) acidic
position is not necessarily sufcient to avoid carbene formation.
Oxidative addition with 1,2,3-trialkylimidazolium salts has been
observed with Pt(0) complexes at C(4) and C(5) positions [259]. It
is well known now that imidazolium cation may react with Pd
Scheme 34. Possible formation of phosphonium salt by reaction of phosphine

ligand with pyridinium.
Scheme 33. Telomerisation of butadiene with Pd complex in [BMMI][NTf2].
24
Scheme 35. Oxidative addition of the imidazolium IL to Ni(0). Mechanism of catalyst deactivation.
catalysed by Ni(0) in [BMI]+ based ILs, active cationic [(carbene)Ni(II)-H]+ catalyst can be generated without any added coactivator by the direct oxidative addition of the [BMI]+ to the
Ni(0). But deactivation occurs rapidly after insertion of ethylene by
a reductive elimination process leading to the formation of 2alkylated imidazolium salt (Scheme 35).
A direct synthesis of NHC-iridium from neat IL has been also
recently reported [266]. The 1,3-dialkylimidazolium halides ILs
inhibit the methoxycarbonylation of iodobenzene with all Pd
precursors used. However with C(2) substituted dialkylimidazolium chloride, the reaction proceeds in a similar way than in [BMI]+
based ILs containing the weaker coordinating anions [BF4] or
[PF6]. A deactivation process has been proposed which involves
the formation either of a Pd(bis-carbene) with phosphine free Pd
precursors, or the formation of a phosphonium salt if phosphines
are present with the Pd precursors used [253]. The formation of
[BMI]2[PdCl4] salts in [BMI][Cl] or Pd(bis-carbene) can also prevent
the nanoparticles to growth and limit activity for CC Heck
coupling reactions. Other evidence of carbene formation is during
the synthesis of nanoparticles of Ir(0) from [Ir(1,5COD)(CH3CN)2][BF4] under D2 and in presence of [BMI][NTf2],
acetone and proton sponge. H/D labelling and 2H NMR reveal the
formation of N-heterocyclic carbene and its coordination with the
Ir(0) nanoparticles [267]. D/H exchange reactions at the imidazolium-d3 cation (80% at the C(2) position and 4% at the C(4) and C(5)
have also been observed in hydroformylation reactions of 1-octene
catalysed by Rh(acac)(CO)2(xantphos phosphine ligand) in
[BMI][NTf2] at 75 8C and under 5 atm of CO/H2. This result
suggests the in situ formation of heterocyclic carbenes. Both
hydroformylation and H/D exchange are catalysed essentially by
the Rh-Xanphos catalyst in the IL. The probability of the carbene

formation is enhanced by the presence of weak bases such as
ethanol [268].
Ni(0)phosphine catalysts have been investigated for the
isomerisation of 2-methyl-3-butenenitrile under biphasic ILorganic solvent conditions (Scheme 36). As the active species is
supposed to be charge free, charged phosphorous ligands are
necessary to anchor the nickel in the IL. Here again, conversions
were much higher with C(2)-methyl versus C(2)-H imidazolium
cation, attesting to the probable formation of a Ni-carbene lessactive species in the case of on-methylated imidazolium [269].
Other evidence of the formation of N-heterocyclic carbenes not
on the C(2) position but on the less acidic C(4) and C(5) positions of
the imidazolium are described in hydrogenation reactions. This
denitively shows that imidazolium-based ILs cannot be considered as innocent solvents and that the use of protected C(2)
imidazolium is not a guarantee that the carbene will not be formed
[270]. In Baylis Hillman reaction, [BMI]+ cation was found to react
with the aldehyde in the presence of a base (Scheme 37) [271]. The
adduct formation is dependent on the nature of the anion present
in the ILs, being more favoured in the case of the [Cl] and [PF6]
anion than with [NTf2].
In conclusion, all these ndings strongly show that ILs based on
imidazolium cations, the ones most employed, may act not only as
solvent but also as reagent in forming N-heterocyclic carbenes
with many transition metal complexes. Therefore, it must be
noted that, in several catalytic processes, the effect of ILs
compared to organic solvents can be explained by the possible in
situ formation of NHC ligand and then new metal complexes with
new activity.
Scheme 36. Isomerisation of pentenenitriles catalysed by Ni complexes in ILs.
25
Scheme 37. Side reaction of the [BMI]+ cation with the aldehyde in presence of DABCO base.
4.3. ILs specially designed for catalysis

Can the changeover from conventional solvents to ILs lead to
signicant inuence on, or even a modication of, the reaction
mechanism? Most catalytic reactions have been evaluated in a
very limited selection of ILs despite the potential huge number of
ILs (including functionalised ILs). Until now, ILs have most be
employed on a trial and error basis rather than on the basis of a
well-founded mechanistic understanding. The inuence of ILs is
not always understood. They often have been designed to fulll a
special task. They even can have multi-functions in the catalysis,
such as solvent, solvent and co-catalyst or catalyst, solvent and
support, solvent and ligands.
4.3.1. Change in mechanism pathway by stabilisation of charged
transition state, active species or ligands
The non innocent role of ionic liquids can be exemplied with
the study of J. Mo et al. on the Pd-catalysed Heck arylation of
electron-rich olens [272]. This reaction has been performed in
imidazolium ionic liquids with a wide range of aryl bromides and
iodides (Scheme 38). Interestingly, the reaction proceeds very
efciently in ionic liquids giving remarkable selectivities compared
with conventional organic solvents (toluene, dioxane, acetonitrile).
Under similar conditions, quantitative conversion were obtained in
[BMI][BF4] to give quite exclusively the a-arylated branched
product (>99/1) whereas mixture of linear and branched
regioisomers were obtained in organic solvents (from 24/76 in
DMAc to 86/14 in DMSO). The authors identied two reaction
pathways involving neutral or ionic intermediates assuming that
the ionic environment provided by the ionic liquid promotes the
cationic pathway and the selective formation of branched product
[273]. Though a great number of catalytic reactions have been
performed in ILs, this is still one of the rare examples which
demonstrates that the ILs are capable of altering the reaction
pathway and then its selectivity.
Another typical example of the inuence of the ionic liquid on
the outcome of chemical reactions is given by the study of the
reaction of toluene and nitric acid [223]. Depending on the ionic
liquid used, nitration of toluene (in [BMI][OTf]), or oxidation of

toluene to benzoic acid (in [BMI][OMs]) or halogenation (in
[BMI][Cl]) were observed. The inuence of the IL anion was also
demonstrated in the case of the isomerisation of 2-methyl-3butenenitrile (2M3BN) into 3-pentenitrile catalysed by Ni(COD)2/
[Ph2P(C6H4SO3][Na] [274]. In [BMMI][Cl], [BMMI][SnCl3],
[BMMI][ZnCl3] or [BMMI][AlCl4] ILs, poor conversion and selectivity were obtained, while in [BMMI][PF6] or [BMMI][NTf2] good
performances were achieved. It was demonstrated by solid state CP
MAS 23Na NMR that an exchange between the sodium in
[Ph2P(C6H4SO3][Na] and the cation of the IL took place and that
this exchange was governed by the Hard and Soft Acid and Base
principle. Hard anions [A] tend to preferentially associate with
the hard [Na]+ cation (Scheme 39). This reaction is driven to the
right in presence of chloride or metallochloride based anions. It
was further demonstrated that the [BMMI][Ph2P(C6H4SO3)]
phosphine gave bad catalytic results.
ILs can also change the reaction selectivity by the promotion of
specic substratesolvent interactions. This behaviour was
observed for the selective hydrogenation of a,b-unsaturated
aldehydes (cinnamaldehyde and citral) catalysed by supported
palladium catalyst (Scheme 40) [275]. Depending on the ionic
liquid nature and reaction conditions, large variations of selectivities were observed. Under identical conditions, [BMI][PF6]
produces hydrocinnamaldehyde with a selectivity of 100% while
with [BMI][OTf] and [BMI][Ac] this selectivity goes down to 91%
and 78%, respectively. The mechanism by which the ionic liquid
works may be associated with the strong interaction of the
carbonyl group with the ionic liquid [276,277]. This interaction
leads to a protection of the carbonyl function, and then a selective
hydrogenation of the double bond. Both the hydrogen bond donor
ability and the nucleophilicity will contribute to any interaction
with the carbonyl. Proper choice of the IL, as well as reaction
conditions are then very important.
Another example is the Ring Closing Metathesis (RCM) in ILs
using the cationic Ru allenylidene complex as catalyst precursor
(Scheme 41). It was already shown that the catalytic transformation of diallyltosylamide in organic solvents was very sensitive to
Scheme 38. Pd-catalysed Heck arylation of butyl vinyl ether by 4-bromobenzaldehyde.
Scheme 39. Cation exchange for ionic ligand operating in ILs.
26
Scheme 40. Selective hydrogenation of cinnamaldehyde in ILs.
Scheme 41. Metathesis of diallyltosylamine in ILs catalysed by cationic Ru-allenylidene.
the nature of the counter anion of the catalyst salt. The reaction
could give the N-tosyldihydropyrole 2 together with the cycloisomerisation and isomerisation by-products 3 and 4 (Scheme 41).
Therefore the catalytic transformation of the diallyltosylamine
was
investigated
with
complexes
[(p-cymene)RuCl(PCy3)5
5C5
5C5
5CPh2][X] in which the anion was varied (X = [PF6],
[BF4], [OTf]) in different [BMI]+ based ILs. One of the rst
questions that was asked when investigating catalysis in ILs was: is
the species that is actually present in ILs the same as the one that
was originally used. These experiments demonstrate that the
catalytic RCM transformation depends on the nature of the counter
anion of both the catalyst and the IL. This suggests that an anion
exchange rapidly takes place and that the catalytic system involves
the anion of the ionic liquid used rather than that of the initial
ruthenium precursor. It was found that the [BMI][OTf] IL affords
the best results in selectivity for 2 as it was the case with triate
ruthenium complex using toluene solvent [278].
To understand the ILs effect, investigations were performed on
the model process of ligand susbtitution on a well-known Pt(II)
complex in ILs, the entering molecule being thiourea named TU
(Scheme 42). The reaction was followed using UV/vis spectroscopy.
In general, as there is an increase in dipole moment in going from
the reactant to the transition state, a decrease in solvent polarity
results in a decrease in the rate of the reaction. In general ILs, the
substitution mechanism was found to follow an associative
substitution similar to that in conventional organic solvents.
However, ILs have a signicant inuence on the course of
Scheme 42. Competing coordination to the Pt centre between thiourea and IL anion
(TU = thiourea and ppp = terpyridine).
the reaction, which differs from that in conventional solvents.

Slower substitutions are found in ILs: rate constant follows
[EMI][NTf2] > [EMI][N(CN)2] > [EMI][OTf] [EMI][EtSO4].
The
study provides evidence of the existence of interaction between
the anion of the IL and the positively charged Pt complex [279].
4.3.2. Solvent for non-charged catalysts
In contrast to charged organometallic species which can remain
immobilized in ILs without any change, the low afnity of neutral
catalytic species with ILs requires to change the catalyst or the
catalyst precursor to anchor it into the ILs. In these cases, the major
efforts have been dedicated to the modication of catalysts with
the aim of increasing their afnity for ILs without altering their
performances. The addition of an ionic tag, cationic or anionic, on
conventional ligands (chiral or achiral) has been largely developed.
The development of ILs incorporating a functional group (ether,
alcohol, nitrile.) can also offer new opportunities to be used as both
solvents and ligands. The best example of this strategy is certainly
given by the hydroformylation of olens in ILs. Recent reviews by
Magna [280] and Haumann et al. [14] describe in detail the
different approaches to immobilize the well-known, non charged,
[HCo(CO)4] or [HRh(CO)4] active hydroformylation catalysts in
different ILs. Besides the development of hydroformylation, the use
of ILs as catalyst-carrying solvents to perform Ru-catalysed
metathesis reactions appear as an approach allowing both (i)
the recycling of the Ru catalyst and (ii) the minimization of Ru
contamination of products [23]. The Ru pre-catalyst is modied by
introducing an ionic tag on the ligand. Most reported examples
concern the modication of the isopropoxystyrene of the Hoveyda
type catalysts, although it is assumed to be the active leaving
carbene group. However, in most of the examples, high catalyst
loadings are employed (in general more than 2 mol% relative to the
feed) so that it is still difcult to estimate the real potential these
biphasic IL systems.
4.3.3. Solvent/stabiliser for nanoparticles

ILs have received attention as alternative solvents and stabilisers
for nanomaterial synthesis, due to their general ease of synthesis,
stability (nonammable, thermally stable), and low vapour pressures [281,282]. Ionic liquids exhibit low interfacial tension that
allows them to adapt to the surrounding reaction media, and their
relative solubility may be tuned by varying their anionic and cationic
components. The controlled and reproducible synthesis of dened
and stable metal nanoparticles (NPs) is of high importance. The NP
synthesis in ILs have been described using different techniques. The
chemical reduction of metal salts or organometallic complexes are
the most extensively described while the decomposition (thermal or
alternatively photochemical decomposition) of the di- and trinuclear metal carbonyls (Fe, Os, Ru) in [BMI]+ based ILs can also lead
to uniform and very small-size nanoparticles [283].
ILs such as [BMI][PF6] and [BMI][BF4] have been used
particularly to synthesise Rh, Ru, Ir, Pd and Ni nanoparticles with
control of size, near-monodispersity, and stabilisation. Usually in
applications involving nanoparticles in catalytic reactions, it is
necessary to use an additional stabiliser or a solid support material.
Here ILs play a dual role of solvent and protective agent to avoid
nanoparticle aggregation. It is assumed that the bulkiness of Il
imidazolium cations favour the electrosteric stabilisation of
nanoparticles, but no concrete information has been available
until now about their possible stabilisation role [284]. However, it
is found that agglomeration can still occur with loss of catalytic
activity, indicating that IL-stabilisation alone can have some
limitations. A good balance between activity, stability and
recyclability of nanoparticles must be found for catalytic applications. Different organic compounds, such as polyvinyl pyrrolidone
polymer (PVP) [285] or N-donor ligands such as phenanthroline
[286] or 2,20 -bipyridine [287,288], triazine or pyrazine derivatives
[289] have proved their efciency as protective agents of Pd (for
phenanthroline) or Rh nanoparticles. The N-donor ligand stabilised
Rh(0) nanoparticles have been successfully applied and recycled in
different hydrogenation reactions involving ILs. Anion effects have
proven to be important. ILs have been put forward to increase the
solubility of PVP in ILs media, hydroxyl-functionalised (Scheme
43). The combination of these hydroxyl-ILs with PVP has helped
stabilise Rh nanoparticles and provides effective and highly stable
catalytic systems for biphasic hydrogenation reactions of styrene.
Other functionalised groups (for instance nitrile, thiol, or ether)
at the N-imidazolium side chains have also been described to
stabilise metal(0) nanoparticles. An example is given with Au(0)
nanoparticles which are characterized by their higher agglomeration tendencies. The stabilisation strength of the standard [BMI]+
based ILs seems to be insufcient. Ether functionalised ILs proved
to be efcient stabilisers and prevent gold nanoparticles from
agglomeration. The surface-enhanced Raman scattering (SERS)
was used as a tool to characterize the species adsorbed on
nanostructured gold surfaces and discloses both the parallel
coordination mode of the imidazolium cation and its stabilisation
role. Surprisingly, no interaction could be detected between the
methylsulfonate anions and the surface of nanoparticles [290].
Very interestingly, it has been recently demonstrated that ILs
could impact the size of nanoparticles during their synthesis. A
correlation between the size of nanoparticles generated by
27
hydrogen reduction in ILs from organometallic complexes (Ni or

Ru) and the self-organisation of the IL has been established. The
decomposition of Ru(COT)(COD) (COD = 1,5-cyclooctadiene;
COT = 1,3,5-cyclooctatriene) under H2 was performed at different
temperature (075 8C) with and without stirring in [BMI][NTf2]
releasing cyclooctane. Nanoparticles with an extremely narrow
size distribution (ca. 1 nm) are obtained at lower T and larger size
at 75 8C (ca. 22.5 nm) without stirring, suggesting that the ILs
limit the crystal growth NPs.
The effect of the temperature on the size of RuNPs is the
opposite in ILs to that normally observed in a THFMeOH mixture
in which low temperatures favour large particle size and,
conversely, high temperatures favour small particle size. It is
assumed that the segregation of Ru(0) occurs exclusively inside the
cyclooctane pockets generated during synthesis; their size
decreases with increasing temperature [291].
So far, the most widely used metal for catalysis in ILs is
palladium, with an increasing number of publications on Stille,
Heck, Suzuki, Sonogashira-Higihara reactions [24]. The main issues
with palladium-catalysed reactions include difculties in catalyst
recycling, poor catalyst stability, decomposition to Pd black and
loss of metal, product separation and isolation and post-reaction
work-up, to cite just a few. ILs could offer great advantages over
conventional solvents. From a practical point of view, adding water
to the reaction mixture can lead to a triphasic system; the salt
(base.HX), formed during the reaction could then be extracted into
the aqueous layer.
In Heck reactions, the use of ILs can be combined with
microwave or ultrasonic irradiation to accelerate the reaction
[292]. Another interesting example is the efciency of the system
based on the functional ionic liquid [BMI][TPPMS] (TPPMS = diphenyl(3-sulfonatophenyl) phosphine) together with [BMI][Ac],
which acts as a base and a solvent, and PdCl2(CH3CN)2 in the Heck
reaction of bromobenzene to ethyl cinnamate. The main advantage
of this system is the synergic effect of imidazolium and the absence
of accumulation of salt as a by-product [293]. In Stille crosscoupling reactions, ILs based on nitrogen anions such as [N(CN)2]
and [NTf2] could ensure high catalytic efciency and facilitate
ligandless reactions. Nitrile functionalised pyridinium cation could
improve catalyst stability and reduce metal leaching [294].
It is difcult to draw succinct conclusions on the impact of ILs
on CC coupling reactions with palladium catalysts, as the effect of
ILs depends on the Pd precursor used, the presence and nature of a
base, and the reactants. It is worth mentioning that ILs often
interact as a ligand in forming either anionic Pd(II) salt such as
[PdX4] in the case of halide based ILs, or in stabilising the Pd(0)
nanoparticle formed in situ. It has been proposed that the ILs could
act as a reservoir of catalytically active Pd species. It may be
highly probable that the reaction proceeds through the oxidative
addition of aryl halide on the Pd nanoparticle surface, and the
oxidized Pd species thus formed are detached from the surface and
enter the main catalytic cycle as a an active molecular species
[295297].
In fact, ILs may display multi-tasks. In the Suzuki reaction
catalysed by PdCl2, it was established that the hydroxylimidazolium functionalised ILs could facilitate the generation/
stabilisation of the active species, favour the activation of the CX
Scheme 43. Examples of hydroxyl-functionalised ILs used to solubilise PVP and stabilise Rh-nanoparticles.
28
bond by H bonding with the X atom and could aid in the solvation
of the salts generated during the reaction, thereby preventing
catalyst poisoning [298].
Table 4
Some examples of concepts developed for sulfur removal from hydrocarbon
streams.
Concept
Added
reactant
Type of ILs
Ref.
Photochemical oxidation
Oxidative desulfurisation
Extractive desulfurisation
H2O2
H2O2
No
[308]
[309]
[310]
Extractive desulfurisation
Alkylation of sulfur
derivative
No
Alkylating
agent
[BMI][PF6]
Protic IL, [MI][BF4]
Phosphoric acidfunctionalised ILs
Fe-containing ILs
Non-cloroaluminate
4.4. Ionic liquids as medium for in situ spectroscopic investigations

The analysis of catalytic systems directly in pure IL or in IL
reaction mixtures, without the addition of a solvent, is rather
scarce although it may be very important to understand reaction
mechanisms in these solvents and to characterize the active
species. Some investigations have been made using mass spectroscopy, infrared spectroscopy and NMR. However, ILs exhibit a
multitude of signals throughout the whole spectral range of
protons that precludes the use of selective pulses for complete
suppression of the solvent signals. Very interestingly, using
Diffusion-Ordered NMR spectroscopy (DOSY), the IL solvent
signals can be suppressed in NMR. The comparatively high
viscosities of ILs can be used advantageously to separate the
solvent and the solute signals. Here, the slower moving molecules
are ltered. This method allows for complete removal of ILs solvent
signals from the 1H NMR of solutes. RMN spectroscopy can be used
without requiring special preparation or deuteration of ILs. This
may become a very useful tool for in situ studies of reactions
performed in ILs [299]. This technique has been applied to
palladium nanoparticle systems dispersed in ILs. Nanoparticles
cannot be detected by NMR, but the determination of diffusion
coefcients of a solvent, such as methanol, and of ILs, and their
changes in presence of the nanoparticles could give some
information about nanoparticle organisation in ILs. For example,
the decrease of IL diffusion coefcients in presence of the
nanoparticles and a basic ligand compared with diffusion
coefcients obtained with ligand-free nanoparticles in ILs was
assumed to evidence for the presence of a Lewis base on the
metallic surface [300]. Raman spectroscopy [252] and infrared
spectroscopy were also shown to be interesting non-intrusive
techniques for in situ characterization of interactions between
catalytic species and ILs. For example, solution of Wilkinson
catalysts [HRh(PPh3)3] were investigated in [EMI][Ac] at different
concentration levels. This study reveals the presence of strong
interactions of the [EMI]+ cation with the catalyst complex, which
was assumed to be through H-bonding of the chloride ligand with
the C(2)-H of the imidazolium [301]. Infrared spectroscopy was
also used to characterize, under variable CO/H2 pressures and
temperatures, the different catalytic intermediates involved in the
Co-catalysed hydroformylation reaction. This study also emphasises the potential of this technique to get better insight of reaction
mechanisms in ILs [302]. Moreover, due to their very low vapour
pressure, ILs enable the application of physical techniques
traditionally restricted to solid state chemistry. It is possible to
investigate the interactions and behaviour of molecular, biological
and macromolecular species in solution using physical and
chemical methods that require special conditions such as highvacuum and have been traditionally used only in solid state
chemistry. The use of TEM to characterize nanoparticles directly in
the ILs without having to separate and precipitate the nanoparticles is another example.
4.5. Removing sulfur from renery streams
In the near future, one may anticipate that the trend will be
reinforced to produce sulfur-free gasoline and diesel. In gasoline
hydrodesulfurisation (HDS) the challenge is to selectively convert
almost all the sulfur-bearing molecules while leaving the olenic
untouched. In diesel, the main issue is the low reactivity of highly
aromatic sulfur species (thiophene, benzothiophene, dibenzothiophene). Above and beyond the large efforts made to improve HDS
[311]
[312]
catalysts and processes, a great deal of work has been conducted on

a variety of possible alternatives. These alternatives involve
oxidative desulfurisation, adsorption, extraction, alkylation, or
complexation. Among these methods, extractive desulfurisation
(EDS) has been covered in many reports. Since the polarity of
aromatic sulde compounds is close to that of sulfur free aromatic
hydrocarbons, the key to an EDS process is to nd an extractant
capable of selectively removing the sulfur compounds without
losing a high volume of feed. In this context, ILs have been reported
as potentially interesting extractants [303]. Compared to molecular solvents, some ILs based on alkylphosphate or alkylsulfate
anions have shown rather high extractability for sulfur derivatives
(Table 4). For aromatic S-compounds, the desulfurisation ability of
ILs is dominated by the cation [304]. But main issues still remain
unsolved like the cross-solubility of hydrocarbons and limited
efciency of ILs. The oxidation of sulfur is one way of improving
extraction selectivity [305]. Commercially available molybdic
compounds can be dissolved in ILs to oxidise S-compounds with
H2O2 under moderate conditions while the ILs play both the role of
extractant and catalyst solvent [306]. Even though the use of ILs
may have some advantages (no need of H2), ILs do not appear to
have an edge over more traditional extractants [307].
5. Concepts for using ILs in homogeneous catalysis
Molecular catalysis is widely used in chemical industry as for
example in oxidation, metathesis, hydroformylation and carbonylation, hydrocyanation, oligomerisation. Some of these reactions
have no heterogeneous counterpart (hydroformylation, hydrocyanation.). However despite its well-established advantages such
as, at least theoretically, using a single-site well-dened catalyst,
high selectivity and activity compared to heterogeneous catalysis,
it suffers from a serious drawback, the separation and recycling of
the catalyst. Catalyst recovery in an active form suitable for
recycling is generally not feasible and the products may be
contaminated with catalyst residues. This is all the more important
as molecular catalysts tend to become more structurally sophisticated. This situation often leads to expensive purication
procedures which disagree with the development of more
sustainable processes. Therefore, there is a need for systems that
can combine the advantages of homogeneous catalysis with
straightforward separation, recovery and reuse of the catalyst. This
situation is common to enzymatic, organometallic and organo
catalysis. Different approaches have been employed to achieve this
goal. The catalyst can be immobilized or contained in either a
solid matrix or in a liquid phase which forms a different
immiscible phase with the reaction products. If gaseous reagents
are present, triphasic or multiphase mixtures may be encountered.
But in the latter case, the key issue is the suitable choice of the
catalyst liquid phase. Many alternative non-conventional solvents
have been developed in which it was possible to take advantage of
molecular engineering to tailor polarity, viscosity, thermal stability
and solubilising power [313,314]. Without being complete, one
can cite peruorinated solvents, supercritical uids and non

aqueous ionic liquids [315]. ILs have been used in various
immobilization strategies: as liquid supports in multiphase
catalysis or in heterogeneous systems (SILP). In these different
uses, ILs have played specic and different roles. In this part of the
review, we will describe the different strategies and concepts of IL
use in catalytic applications, bearing in mind the possibility of
applying these processes in a continuous mode on an industrial
scale. We will evaluate the scope but also the limitations of these
different approaches. We will see that some limitations can
provide opportunities for new developments or new chemistry.
Rather than describing all the reactions performed in ILs, the
authors have preferred to describe selected examples.
5.1. Multiphasic IL systems
In homogeneous catalysis, the catalyst separation and recycling
is an important issue. The recycling can be operated by chemical
transformation or by direct distillation, depending on the catalyst
and its stability. Its recycling can also be performed using a biphase
liquid/liquid system [316]. Initially developed for the aqueous
biphase system, this concept was further extended to other media
than water including ILs. Most organic substrates generally do not
have sufcient solubility in the catalyst phase, particularly in water,
to give practical reaction rates in catalytic applications, or in many
cases there are incompatibilities between the catalyst and the
solvent. Thanks to the wide range of available ILs (cationanion
combinations), one may nd that ILs offer an attractive option to
improve the reactants solubility in the catalyst phase. In addition, it
is often possible to nd a biphasic IL/organic system for which the
catalyst is dissolved and immobilized in the IL. The ideal situation is
obtained when the IL displays partial miscibility with the substrates
and when the products have negligible miscibility with the IL (Fig. 6).
Separation is then obtained by decantation which simplies the
process scheme and limits the risks of catalyst decomposition during
distillation. This option can also provide opportunities for new
chemistry, for example, by shifting equilibria through in situ
extraction or by improving selectivity for primary reaction products
when there is a preferential solubility of one reactant in the catalyst
phase and then in situ extraction of reaction intermediates in the
other phase. This can be a way to operate separative catalysis and
process intensication. This improvement of selectivity has been
exemplied for transformations where consecutive reactions such
as olen oligomerisation or selective diene hydrogenation need to be
avoided.
5.1.1. Some challenges and opportunities of multiphasic systems
One of the main issues of the applicability of this concept is the
immobilization of the catalyst in the ionic liquid phase. When
Fig. 6. The IL-liquid/liquid-biphase concept (M = monomer, M-M = dimer, M-MM = trimer).
29
active catalysts are charged species (cationic or anionic), this goal

can be achieved without the need for specially designed ligand
provided that the active species remain charged during all the
catalytic cycle. However in some cases, cationic complexes could
exist in equilibrium with molecular species. For non charged
catalysts, an efcient immobilization generally requires the use of
ligands-bearing ionic tags. This adjustment of ligands to ILs can
result in a modication of the catalytic system performance which
is not always easy to anticipate (see Section 4 of this review).
Furthermore, whatever the ionic ligand used, deactivation may
occur by displacement of the ionic ligand with one of the reactants.
This may result in a deactivation process due to leaching of the
active species in the organic phase. To prevent such metal loss,
large amounts of ligand are used, which often has a detrimental
effect on the reaction rate.
Multiphase systems involve not only chemical interactions of
the catalyst with the solvent, but also main issues such as
solubility, partition coefcient, mass transfer (viscosity of ILs is
generally much higher than that of organic solvents) which can be
limiting steps in kinetics and can dene some thermodynamic
constraints. For example, the solubility of gases in ILs is an
important parameter for reactions involving gaseous reactants
(hydrogenation, hydroformylation, oxidation.). Hydrogen [317],
oxygen and carbon monoxide display, in general, very low
solubility in ILs with the gas mole fraction of the order of 104
near ambient conditions [318].
When the products are partially or totally miscible in the ionic
phase, such as aldehydes or alcohols in hydroformylation,
separation is much more complicated. One advantageous option
may be to perform the reaction in a single phase, thereby avoiding
diffusional limitation, and to separate the products in a further step
by extraction. We have recently applied this concept to the cobaltcatalysed hydroformylation of olens associated with an original
catalyst recycle [319]. In this work, the recycling of the catalyst is
based on equilibria between neutral and ionic species when
different reaction conditions (T, P) are applied. In the absence of
CO/H2 and under atmospheric pressure, the Co2CO8/Pyridine
system used is essentially present in its ionic forms [Co(Pyr)6][Co(CO)4]2 and [PyrH][Co(CO)4] [320,321]. While increasing
pressure and temperature, [HCo(CO)4] is generated. Owing to its
high solubility in heptane, one might expect it to be extracted in
the upper organic phase where it operates without any mass
transport limitation. Reducing the operating conditions from
100 bar CO/H2 and 130 8C to atmospheric CO/H2 pressure and
room temperature decreases the stability of [HCo(CO)4]. The latter
species tends to dimerize into [Co2(CO)8] or reacts with pyridine to
form [PyH][Co(CO)4] by direct neutralisation. The [Co2(CO)8] dimer
can then react with free pyridine to produce another ionic
[Co(Pyr)6][Co(CO)4]2 species. Because of their high afnity for the
ionic medium, both these ionic species are extracted and
immobilized in the ionic phase. The products can then be separated
by decantation, thanks to the addition of a non solvent in the
decantation section. From a practical viewpoint, the addition of a
non-solvent can result in cross-contamination, and it has to be
separated from the products in a supplementary step (distillation).
More interestingly, unreacted organic reactants themselves (here
weakly polar olens) can be recycled to the separation step and can
be used as the extractant co-solvent. The ionic liquid containing
the cobalt catalyst precursors can be recycled into the reaction
section and reactivated under CO/H2 pressure (Fig. 7).
5.1.2. Use of scCO2 as the transport vector for substrates and products
The use of a co-solvent poorly miscible with the IL (water or
organic solvent) to extract the reaction products diminishes the
overall simplication of the recycling and can go as far as causing
contaminating the IL. The use of supercritical uids in particular
30
Fig. 7. Cobalt-catalysed hydroformylation of olens. A new concept for catalyst

recycle (1: reaction, 2: pressure/temperature decreasing, 3: separation section).
CO2 (scCO2) proved to be an interesting alternative to common

organic solvent because of its nontoxic nature, its recoverability
and ease of separation. It has been experimentally demonstrated
that a wide variety of substrates could be removed from [BMI][PF6]
with scCO2 [276]. ScCO2 dissolves quite well in ILs while ILs cannot
dissolve in scCO2, which provides a means of ILs recycling without
product contamination. Continuous-ow catalytic systems based
on the combination of IL [BMI][PF6] and scCO2 employed as the
transport vector for the substrates and products, was reported for
the rst time for 1-octene Rh-catalysed hydroformylation using
ionic phosphine [322]. In the continuous ow process, the
substrates are transported into the reactor and the products
removed using scCO2 (Fig. 8). But it was also discovered that high
reaction rates could be obtained only for alkenes exhibiting good
solubility in ILs and under very high pressure, to make scCO2 a good
solvent for the products. The solubility of alkenes in ILs depended
considerably on the length of the alkyl chain on the ILs
imidazolium cation. 1-octyl-3-methylimidazolium bis(triuoromethyl)sulfonamide [OMI][NTf2] was found to give optimum
performance when associated with [1-alkyl-3-methylimidazolium][Ph2P(3-C6H4SO3)] as catalyst ligand [323].
The concept of ILs/scCO2 was extended to other reactions such
as hydrogenation [324,325], hydrovinylation [326], as well as to
bio-catalysed reactions [327]. Another recent example of continuous reaction using ILs as a stationary reaction phase, and using
scCO2 as a mobile non reactive phase is the acylation of aromatic
hydrocarbons (such as anisole) catalysed with In(OTf)3, a soft
Lewis acid [328]. The [1-Butyl-4-methyl-pyridinium][NTf2] IL is
chosen because of its negligible extraction in scCO2. One advantage
besides that of IL recycling and product extraction is that the
presence of compressed CO2 decreases the IL viscosity, which may
facilitate mass transfer during catalysis. Another possible opportunity associated with the use of CO2 is to bring about the
separation of water from hydrophilic ILs such as [BMI][BF4], by
adjusting the pressure and temperature. However, the separation
of water cannot be complete and the reaction of CO2 with water to
form carbonate is probable and may induce a salting-out effect
responsible for aqueous phase separation. It has been experimentally shown that the addition of a salt such as Na2CO3 (0.28 g) in
water (1.25 mL) to the hydrophilic [BMI][BF4] IL (2.5 mL) leads to a
biphasic system below 50 8C with the inorganic salt remaining
preferably in the aqueous layer. This is a way of removing the salt
by-products generated in the Pd-catalysed Suzuki reactions [261].
Other interesting ideas have been proposed for the recovery of
hydrophilic ILs from their mixture with water [84].
5.1.3. Demonstration of continuous catlytic performances
Batch-mode screening experiments are very often used to
identify the best combination of IL, catalyst precursor, ligand,
operating conditions and product separation. However, data
concerning the recycling IL catalyst phase, the lifetime of the
Fig. 8. Continuous ow homogeneous catalysis using a supercritical uidionic

liquid biphasic system (reproduced by permission of the Royal Society of Chemistry
[323]).
catalytic system (leaching aspect), the stability of the IL towards

feedstock, products and process conditions, which are crucial for
biphasic system development, cannot be obtained with batchmode tests. Continuous experiments must be designed to obtain
this information. Very few examples of continuous ow rate
experiments have been described in literature.
Continuous ow reactions in biphasic IL systems have also been
demonstrated in a well-stirred reactor (Section 6.1.1). One might
also mention the reaction performed in loop reactor with
integrated IL separation (Fig. 9). This experimental tool has been
used at bench scale to demonstrate the feasibility of different
reactions performed in biphasic systems (for Ni-catalysed dimerization see [329]). The last example is the multiphasic hydrosilylation of olens. This reaction has been covered in several
publications, using ionic liquids as catalyst solvent. But the
industrial attractiveness was recently demonstrated for the
hydrosilylation of 1-hexadecene with oligosiloxanes using pyridinium tetrauoroborate as the IL. Average conversions of >86%
(with K2PtCl4) and >82% (with PtCl2(PPh3)2) could be achieved
[330,331]. Another example is given with the hydrosilylation of
allyl chloride with trichlorosilane to form trichloro(3-chloropropyl)silane. This industrial reaction is technically challenging
because of the use of trichlorosilane and the formation of
undesirable side products such as tetrachlorosilane and propylene
which can undergo consecutive reactions. This has been described
in continuous mode using a loop reactor, PtCl4 as Pt source, and
[NTf2] based ILs (i.e. [EMMI][NTf2]) due to its stability against
chlorosilane. The removal of reaction heat was achieved thanks to a
high heat exchange surface to reactor volume ratio. In this system,
the reactor is fully back-mixed and can be considered as a
continuous stirred-tank reactor (CSTR). The biphasic mixture (IL
and reaction products and substrates) is circulated in the loop at a
Fig. 9. Continuous hydrosilylation loop reactor (reproduced from [332] with

permission of Wiley).
31
Fig. 10. Preparation of acidic IL anchored on silica.
high ow rate. Decantation and separation of the products from the

IL phase takes place in a gravity separator built in the loop. Using
this reactor concept, it could be demonstrated that very good
immobilization of Pt in IL could be achieved without any specic
ligand. The selectivity to the desirable product was stabilised
around 6271% for conversions ranging from 50 to 70% [332].
Numerous other examples of IL-liquid/liquid-biphase systems
can be described. Some of them are detailed in the rst part of this
review. For an exhaustive list, readers may refer to the recent
review by Parvulescu and Hardacre which covers this aspect very
well [8].
5.2. Supported ionic liquid phase system (SILP)
5.2.1. ILs supported on solid inorganic solid
In parallel to the development of ILs for biphasic liquid/liquid
catalysis, strategies for immobilizing ILs on a solid support have
been addressed. This concept was developed, among other things,
to minimize the amount of sometimes expensive ILs and to allow
the applicability of ILs in continuous-ow-operated xed-bed
processing.
Acidic chloroaluminates were rst supported on solid inorganic
material. The immobilization of the IL consisted in the addition of a
pre-formed chloroaluminate IL to a previously dried and calcinated
support (500 8C for 3 h). The excess of IL on the support was then
eliminated by extraction with dichloromethane [333]. After
drying, this material was applied for alkylation of aromatics
(benzene, toluene, naphthalene and phenol) with 1-dodecene.
Some catalyst deactivation occurred as the supported IL system
was operated in continuous mode. This loss of conversion with
time was assumed to be the effect of heavy products which block
the active sites of the solid material from further reaction. An
alternative method for supporting acidic chloroaluminate ILs is to
chemically bond the Lewis acid on an inorganic support already
functionalised with an ammonium, imidazolium or pyridinium
chloride moieties [334336]. This approach can improve the
efcient immobilization of the IL especially when the catalytic

reaction is performed in a liquid phase (Fig. 10).
In 2002, C. P. Mehnert at ExxonMobil developed quite a similar
approach for olen hydroformylation [337]. The immobilization
strategy involves a support material (silica gel) that is modied
with a monolayer of covalently anchored fragments of 1-n-butyl3-[3-(triethoxysilanyl)propyl]-4,5-dihydroimidazolium.
Treatment of this surface with additional ionic liquid results in the
formation of a multiple layer of free ionic liquid which serves as the
reaction phase in which the homogeneous catalyst is dissolved
(Fig. 11). Batch 1-hexene hydroformylation experiments were
performed using Rh(CO)2(acac) and ionic tagged ligand
([TPPTS][Na], [TPPTS][BMI]) as catalyst precursor. For the different
supported ionic liquid systems studied, increased reaction rates
were observed due to higher concentration of the active rhodium
species at the interface and the larger interface area of the solid
support in comparison to the biphasic system. This work was
further extended to olens hydrogenation with cationic rhodium
catalyst [338,339]. The resulting catalysts exhibited high activity
and outstanding stability. However, no solution was proposed for
catalyst regeneration.
Similar studies were conducted in continuous mode for the gasphase hydroformylation of propene [340]. But in this case the
supported system was prepared by direct impregnation of a
unmodied silica gel with a methanol solution containing
Rh(CO)2(acac), the ligand (sulfonated Xantphos, L/Rh = 1020)
and the ionic liquid ([BMI][n-C8H17OSO3]). The IL coating
constitutes only a thin lm which is conned to the surface of
the solid by physisorption (Fig. 12). The performance of the
optimised catalytic system remained stable up to 5 h before a
decrease in activity and selectivity was observed. This work was
later improved by a careful choice of both the IL, the ligand and the
properties of the support [14,341]. The Rh/SILP catalyst performed
similarly to a homogeneous catalyst with demonstrated long-term
stability. This long-term stability appeared to decrease when liquid
substrates were used [14]. In that conguration, hydroformylation
Fig. 11. Supported Ionic Liquid Phase (SILP) catalysis concept for olen hydroformylation. The IL is conned on the surface of silica through covalent anchoring (reprinted with
permission from [337]. Copyright 2009 American Chemical Society).
32
Fig. 12. Schematic representation of SILP: the IL is conned on the solid support by
physisorption (example of the MeOH carbonylation)reproduced from [343] by
permission of The Royal Society of chemistry.
activities drop due to the limited diffusion of H2 and CO into the

liquid lled pores of the support and to the solubility of the IL in the
reaction products which produced gradual leaching of both the IL
and Rh catalyst. A concept using the combination of SILP and scCO2
was envisaged to circumvent these limitations [342]. Results
clearly demonstrate that scCO2 improves the diffusion of both the
substrate and CO/H2 within the supported ionic liquid. It also
permits the continuous extraction of the by-products. The use of
SILP technology has been extended to several reactions and solid
supports such as methanol carbonylation catalysed by rhodium
complexes [343] or Friedel-Crafts alkylation [344]. Despite some
demonstrated advantages such as minimization of mass transfer
limitations due to very short diffusion distances in the supported
ionic liquid lms, maximum utilisation of IL and catalyst, xed bed
technology applicability, it still suffers from some limitations. To
cite just a few, one may mention that substrates and products
should preferably be gaseous, accumulation of heavy by-products
in the solid is possible and can lead to catalyst deactivation, no easy
solutions for the regeneration of the solid catalyst bed are
envisioned.
5.2.2. ILs supported on hybrid organicinorganic material
Hybrid organicinorganic silica materials containing imidazolium and SiC covalently bonded moiety have been synthesised
according to conventional solgel procedures in the presence of
surfactant template and tetraethylorthosilicate [345]. These mesostructured materials have recently been used as supports to
immobilize transition metal complexes such as Pd for Suzuki crosscouplings with aryl bromide reactions. In the latter reaction, in situ
formation of NHC-stabilised nanoparticles are suspected [346].
5.2.3. ILs supported on organic polymers
The development of other supports than silica was also
investigated with notably the use of a polystyrene functionalised
resins [347]. These supported ILs were synthesised from Merrield
resins, with many opportunities for the variation of the linker
length, the loading level of the IL portion and the nature of the IL
anion (Fig. 13). The catalytic properties of this new material were
examined through the study of nucleophilic uorination and
bromination of 2-(3-methanesulfonyloxypropyl)naphthalene as a
model compound. Best results were obtained with the PSIL
(Polystyrene supported ionic liquids) presenting the longest linker
(hexyl or dodecyl) with BF4 as counteranion. The desired
uoroalkane and bromoalkane were produced almost quantitatively. The effect of the PSIL loading (mmol of IL per gram of PS
resin) was also investigated. It appeared that large PSIL loading
produces the best result for uorination reaction (matrix effect)
whereas for bromination reaction, the reverse tendency is
observed (both matrix and site isolation effects). Interestingly,
no reaction occurred when PS with no IL portion is used.
Poly(ethylene glycol) (PEG) polymers have received rising
interest as a reusable solvent medium for organic synthesis and
catalytic process. The combination of PEG with ILs was realised by
the synthesis of PEG-functionalised ILs. These ILs have proved to
display interesting chemical and physical properties [348]. Their
application in catalysis is not very developed but may offer
interesting opportunities [349]. PEG-supported ILs have also been
shown to be efcient media for catalytic reactions such as CC
coupling with Pd(OAc)2, thus providing a ligandless recyclable
system [350].
5.3. Switchable polarity solvents
Some specially-designed solvents may reversibly switch their
polarity from a low polarity form to a higher polarity form when a
trigger is applied. In this concept, the modication of the solvent
polarity induces solubility changes of products and/or catalysts,
making their separation and purication feasible. For the concept
of switchable solvents, the polarity change is performed by
addition of CO2 to a mixture of two liquid components, either
amidines and an alcohol [351] or primary amine/amidine mixture
[352] or secondary amines (without amidines) [120]. In both cases
a carbamate salt forms which can then be assumed as an ionic
liquid (Fig. 14).
This concept has been applied recently as a post-treatment step
in the alternating polymerization of cyclohexene oxide with CO2
[120]. The polymerization reaction is performed using [PPN]-N3 as
co-catalyst and Cr(salen)Cl as catalyst under 35 bar of CO2 without
solvent (Scheme 44). After the polymerization section, the CO2 was
released and the polymer and the catalyst dissolved in the NHEtBu.
When CO2 is bubbled through this new mixture, the secondary
amine is converted into the polar carbamate salts in which the
polymer precipitates. The colour of the solution indicates that the
catalyst remains mainly in the solution. Slight colouration of the
polymer is nevertheless observed but can be corrected by several
SPS cycles. Remarkably, the chromium catalyst can be recovered by
distillation of CO2 and the amine, and nally reused for
polymerization.
Fig. 13. Polystyrene supported ionic liquids (PSIL).
33
Fig. 14. Switchable solvents.
Scheme 44. Alternating polymerization of cyclohexene oxide with CO2.
In an equivalent approach, Jessop et al. reported the polymerization of styrene using DBU and 1-propanol as the SPS system
[121]. In that case, CO2 and N2 at 1 bar were used as polymer
miscibility and immiscibility triggering agents (Fig. 15). Interestingly, the molar ratio of DBU and 1-propanol was 1:2.5, the excess
of 1-propanol reducing the viscosity of the polar form (75 7 cP)
which then facilitates ltration of the polymer. This solvent can be
used several times (4 cycles) with nevertheless the need for fresh
solvent addition in order to compensate losses during ltration.
Recently a new class of one-component, thermally reversible,
neutral to ionic liquid solvents were described [353]. Its structure
is based on siloxylated amines which introduce weak Lewis acid
functionality (Scheme 45). The ionic liquids produced under a CO2

atmosphere are reversed to their molecular precursors at moderate
temperatures (around 120 8C). This new switchable solvent system
was applied to the recovery of alkanes from heavy crude oil. For the
example described, a mixture containing 50% wt of crude oil in
TESA (triethoxysilylpropylamine) is used. The single-phase homogeneous system obtained is then transformed by CO2 bubbling. The
viscosity increases as the carbamate ionic liquid forms. Centrifugation is then needed to separate the puried crude oil (top
phase) from the IL containing the oils impurities (bottom phase).
Heating the IL phase up to 120 8C regenerates the TESA to its
neutral form, which can then be recycled.
Fig. 15. Styrene polymerization in DBU/PrOH switchable solvent.
Scheme 45. Example of supported switchable solvent system.
34
Fig. 16. Thermoregulated catalysis using peruorinated solvent.
5.4. Thermoregulated ILs

Successfully introduced for biphasic catalysis using peruorinated solvents, the concept of thermoregulated catalysis has been
the subject of many variations and extensions [354]. In the initial
concept, the catalyst is dissolved in a uorous solvent where the
substrates are not soluble if the reaction is maintained at room
temperature. By heating the mixture, a single-phase homogeneous
system is created making possible the formation of products
without any mass transfer limitations. Finally, the separation of the
products from the catalytic uorous phase can be operated by
cooling down the mixture (Fig. 16).
Thermoregulated IL-based systems were developed in analogy
to this concept. The temperature-dependent reversible phase
separation of ILs was exploited for this purpose. This phenomenon
can be obtained either for ionic liquid-aqueous system [355], or
ionic liquid-organic liquid systems [202,356]. In 2001, the study of
the transition-metal-catalyse hydrogenation of a water-soluble
substrate was described [357]. The ionic liquid used ([OMI][BF4]),
containing [Rh(h4-C7H8)(PPh3)2][BF4] catalyst forms a separate
layer to water containing 2-butyne-1,4-diol. Under reaction
conditions (60 atm, 80 8C) a single phase forms. On cooling to
room temperature, two phases reform, with the ionic liquid phase
containing the catalyst and the aqueous phase containing a
mixture of 2-butene-1,4-diol and butane-1,4-diol products that
can be removed simply without catalyst contamination.
Olen hydrosilylation was also described on the basis of the
thermoregulated IL concept [358,359]. In this work, the Wilkinsons catalyst [RhCl(PPh3)3] was used in association with various
N-alkylpyridinium or N,N-dialkylimidazolium ILs (Scheme 46). All
the ILs used were solid at room temperature. Before reaction, the
catalytic system is prepared by mixing the IL with [RhCl(PPh3)3] at
100120 8C. After cooling down to room temperature, a solid was

ground up for use as the catalyst. Under hydrosilylation reaction
conditions, the Rh/IL solid becomes a liquid and the reaction can
be conducted as a liquidliquid biphasic system. After completion
of the reaction, the solid Rh/IL reforms and can then be efciently
separated and recycled.
Recently, hydroformylation of 1-dodecene was also investigated [360]. In a classical IL biphasic system, the transformation of
1-dodecene remains quite challenging as the solubility of 1dodecene in ILs is low even under process conditions. In this
context, thermoregulated ILs can clearly bring some advantages. In
the work of Tan et al., several ILs derived from quaternary
ammonium alkylsulfonates with polyether chains were synthesised (Scheme 47). In combination with toluene and heptane, these
ILs can form thermoregulated IL systems. For example, when the
hydroformylation of 1-dodecene is conducted in ILPEG750, nheptane and toluene, the phase containing Rh/TPPTS complex
is immiscible with the upper organic phase at room temperature.
The miscibility of the system is 108 8C. On heating the reaction
mixture above this value, the system becomes monophasic and the
reaction proceeds homogeneously. The conversion of 1-dodecene
is increased sharply if compared to reactions performed at 100 8C.
The system switches back to two phases on cooling down to room
temperature. Under optimum conditions, the conversion of 1dodecene and yield of aldehyde are 99% and 97%, respectively. In
addition, the catalyst could be easily separated from products by
phase separation and efciently recovered.
5.5. Phase transfer catalysis
One of the essential roles of classical phase transfer catalyst is to
displace an inorganic reagent from the aqueous phase into the
organic phase, thus enabling the organic substrate to react with the
transferred anion and form the product in the organic phase
reaction. ILs can play this role with the unequivalent property of
being totally tunable for the targeted reaction. For example, Wang
et al. described a [BMI][PF6]/water biphasic system for the phase
transfer epoxidation of electron-decient a,b-unsaturated carbonyl compounds [6,361]. The reaction takes place in the presence of
NaOH as a base and hydrogen peroxide as an oxidant. The process
can be described following the mass transfer model shown in
Fig. 17. Under the mild conditions applied, the [BMI][PF6]/water
system was more efcient than the traditional CH2Cl2/water
system. By optimising the reaction conditions, including reaction
time, temperature, the amount of oxidant and sodium hydroxide,
100% conversion and 98% selectivity could be achieved in the
epoxidation of mesityl oxide.
Scheme 46. Hydrosilylation of olens with triethoxysilane (R5

5C6H5(styrene), R5
5C4H9 (1-hexene), R5
5C6H13 (1-octene), R5
5C9H19 (1-undecene)).
Scheme 47. Thermoregulated ionic liquid catalytic process for olen hydroformylation.
35
Fig. 17. Mass transfer model for epoxidation in [BMI][PF6]/water PTC system (Q+ = dialkylimidazolium cation; M = sodium; X = hexauorophosphate anion).
Scheme 48. Enantioselective Michael addition of dimethyl malonate.
The inuence of the ILs nature was studied on the phase

transfer-catalysed enantioselective Michael addition [362]. This
reaction is promoted by a quaternary derived ammonium salt from
quinine (Scheme 48). In terms of yield and enantiomeric excess
(ee), the best results were obtained using the more hydrophobic IL,
[BMI][PF6]. Surprisingly, the ee obtained in ILs derived with
imidazolium cation (a26
D < 0) were reversed with those obtained
in [N-butylpyridinium][BF4] or classical organic solvents
(a26
D > 0). The factor responsible for the reversal of enantioselectivity was ascribed to the nature of the IL cation as previously
demonstrated for the enantioselectivities of lipase catalysed
transesterication [363].
New candidates for phase transfer catalysis were described in
2006 [364]. They consist of uorous quaternary phosphonium salts
bearing four ponytails. After being applied in a model phase
transfer reaction (picrate extraction) to dene their ability as
transfer agent, they were applied for the nucleophilic substitution
of alkyliodide (Fig. 18). Using only 10% mol of the phosphonium
salt [(CF3(CF2)7(CH2)2)3(CF3(CF2)5(CH2)2)P]+[I] as the phase
transfer agent, conversion of compound 1 can reach 95% whereas
no reaction occurred in the absence of the phosphonium salt.
6. Overview of industrial applications and economic issues

Since the early days of ionic liquids in electrochemistry, the
scope of their applications has been extended to many domains
and is now much broader than assumed. Following this
tremendous development associated with the commercial availability of ILs, the industrial applicability of ILs rapidly appeared as
an important aspect as demonstrated by the accelerating number
of patents associated with the keyword IL. The patents (and
publications) often describe numerous applications such as
catalysis with increased rates and yields, recovery of catalytic
systems, use of ILs as solvents that can reduce environmental
impacts and that lead to more energy-efcient separation. ILs
appeared as novel solutions to the chemical industry. However,
despite these signicant benets, their translation into viable
industrial processes is far from being obvious and the industrialization of IL technologies is rather slow, particularly in the eld of
catalysis. For the industrial use of ILs, some major issues must be
addressed such as IL synthesis scale-up, purity, stability, toxicity,
recycling, disposal and price and may constitute barriers to IL
process commercialisation (see Section 6.2). Several pilots or
Fig. 18. Substitution of alkyliodide using a phosphonium salt as catalyst.
36
industrial processes using ILs were nevertheless publicly

announced. It is probable that some other processes have been
developed but the information has not been made public. In recent
literature, good reviews describe these examples in a fully detailed
manner [11,365].
6.1. Selected examples of industrial/pilot scale applications of ILs
In this paper, we have essentially mentioned the applications
developed in relation with catalysis. A non exhaustive list is given
below. Examples in the elds of electrochemistry, energy and
engineering uids are listed in a summary table with references to
the more representative work.
6.1.1. Dimerization and oligomerisation of olens: IL as solvent and
Ni-co-catalyst
6.1.1.1. The Difasol process (Axens). Since the mid-1970s, IFP
developed the DimersolTM process (Dimersol-E, -G, and -X) that
upgrades light olens by dimerization (respectively, ethylene,
propylene and butenes). The Dimersol-XTM produces mixtures of
low branched octenes which are good starting materials for
isononanol production (intermediates in the plasticizer industry).
For this homogeneous process, the reaction is operated without a
solvent in a unique liquid phase using a Ziegler-type catalyst based
on nickel and activated with an alkyl-aluminium co-catalyst [366].
The DifasolTM process can be considered as the biphasic analogue
of the Dimersol-XTM process. The reaction takes place with the
same nickel catalyst precursor using chloroaluminate ionic liquids
as the solvent (Eq. (1)). When associated with a chloroalkylaluminium activator like EtAlCl2, this mixture can react to form ionic
liquids presenting mixed anions (Eq. (2)) [252,367]. The ionic
liquid can then act as both solvent and co-catalyst (Eq. (3)). As the
activity of the nickel system depends on the Lewis acidity, an
accurate adjustment of the EtAlCl2/AlCl3 is required to optimise the
efciency of the catalytic system. The best results were obtained
from [BMI][Cl]/AlCl3/EtAlCl2 (1:1.2:0.11) mixtures.
AlCl3
AlCl3
BMICl BMIAlCl4 BMIAl2 Cl7
(1)
AlCl4 EtAlCl2 $ EtAl2 Cl6
(2)
NiCl2 BMIEt2 Al2 Cl5 $ Ni-EtEtAlCl3 BMIAlCl4
(3)
Thanks to its ionic nature, the Ni catalyst is dissolved and remains

immobilized in the IL, without additional ligand, where the
reaction products are poorly soluble. The reactants miscibility
remains adequate to ensure reaction. No catalytic activity occurs in
the organic phase. No co-miscibility was observed between the
products and the ionic liquids, product separation could be
operated by simple decantation of the two phases. In order to
demonstrate the recyclability and the life time of the catalytic
system, a continuous ow pilot plant was operated using a wellstirred reactor followed by a decanter [368,369]. The experiments
were run with a representative industrial C4 Rafnate-2 cut
composed of 70% butenes (27% of which is 1-butene) and 1.5%
isobutene (the remaining being n-butane and isobutane). The test
was conducted continuously over a period of 5500 h after which it
was deliberately stopped. No additional fresh ionic liquid was
required during the test. No ionic liquid can be detected in the
products. This continuous pilot test denitely demonstrated the
stability of chloroaluminates under dimerization conditions. The
main advantage of biphasic DifasolTM lies in the easy product
separation that can be performed in a subsequent step. The
product separation by settling does not require heating and results
in energy savings plus reduced catalyst consumption. Another
Fig. 19. Dimersol + Difasol package reaction: (1) Dimersol reactor(s), (2)
Vaporisationcondensation, (3) Difasol reactor.
interesting result is the excellent activity obtained when diluted

feedstock is used. With Dimersol-XTM technology, olen conversion is highly dependent on its concentration in the feed. On the
contrary, DifasolTM performance is maintained over a wide range of
butene concentrations, with the same catalyst consumption. The
Difasol reaction section and settling sections can ideally be
integrated as a nishing reaction section after a rst homogeneous
Dimersol reactor (Fig. 19). This conguration is particularly
adapted for the treatment of diluted feed for which the DifasolTM
efciency has been demonstrated. This arrangement ensures more
efcient overall catalyst utilisation and an increase in the yield of
octenes by about 10 wt% [369].
The main DifasolTM benets can be summarised by the
following main points:
the overall yield in C8 octenes can be 10% higher than in the
homogeneous process;
the nickel consumption is less than in the homogeneous process;
no ionic liquid can be detected in the products;
a much smaller reactor, operated with biphasic system, can give
the same throughput of octenes.
The DifasolTM process has been extended to the selective
dimerization of propene. In that case, the addition of bulky and
basic phosphine ligands such as triisopropylphosphine or tricyclohexylphosphine is necessary to drive the reaction to the
selective formation of 2,3-dimethylbutenes (2,3-DMB-1 and 2,3DMB-2). 2,3-Dimethylbutenes are especially important since they
can be used as key starting olens for ne chemical intermediates
[370372]. The reaction can be performed in acidic chloroaluminates with Ni(II) salt, trialkylphosphine and alkylaluminium as cocatalyst. The phosphine effect can be maintained providing a right
adjustment of the ionic liquid acidity [373,374]. The reaction was
carried out in a semi-continuous way for more than 50 h [375,376].
The main issue was to maintain constant the 2,3-DMB selectivity
over time, because of a competition for the basic phosphine
between the soft Ni catalyst and the hard aluminium chloride
potentially present in the acidic ionic liquid. Aromatic hydrocarbon
proved to be ideal basic additives to prevent the loss of 2,3-DMB
selectivity. Due to their poor basicity, they do not strongly interfere
with the Ni active centre and do not decrease the catalytic activity.
They can be considered as buffers, thereby stabilising the
phosphine effect. In that way, the hexene selectivity was
maintained constant around 7580 wt% hexenes/total products
and the 2,3-DMB-1 was maintained at 7075 wt% relative to the
total hexene content.
6.1.1.2. Oligomerisation of olens for synthetic lubricants production. Alpha-olens may be oligomerised to prepare synthetic
lubricating oil base stocks which have desirable lubricating
properties such as a low pour point and a high viscosity index.
In 1997, BP Chemicals described a process for the oligomerisation
of a mixture of a-olens (typically C6-C10) using acidic ionic
liquids [377]. Typical ionic liquids used are based on [EMI][Cl]/
37
Scheme 49. LAB production.
AlCl3 in a 1:2 molar ratio. In that case, kinematic viscosity at 100 8C

is usually below 20 cSt. Some years later, Chevron disclosed that it
is possible to obtain oligomers with higher kinematic viscosity by
performing the oligomerisation reaction in the absence of organic
diluent [378380]. By this way, polyalphaolens having viscosities
in excess of 22 cSt and even 30 cSt may be readily prepared.
Starting from 1-decene and [HNMe3][Cl]/AlCl3 in a 1:2 molar ratio,
kinematic viscosity was 31.6 cSt. According to a recent information, this process would be applied at a pilot scale to produce
commercial quantities of over 450 tons of polyalphaolens [365].
6.1.2. Friedel-Crafts alkylation and acylation of aromatic
hydrocarbons: IL as solvent and catalyst
6.1.2.1. LAB production. Alkylation of benzene with linear olens
(C10C14) is a well established industrial application (Scheme 49).
The linear alkylbenzenes produced (LABs) are used as intermediates in the manufacture of surfactants and detergents. Traditional
processes use acid catalysts such as AlCl3 and HF which suffer from
both poor catalyst separation and recycling.
Akzo-Nobel developed specic ILs based on triethylamine
hydrochloride
and
aluminium
chloride
(2AlCl3 + [HNMe3][Cl] $ [HNMe3][Al2Cl7]). These ILs can be cheaper alternative
to imidazolium-based salts and can be applied in a similar manner
[381]. These ILs were specially applied to the alkylation of benzene
with 1-dodecene [382]. It appeared that higher 2-dodecylbenzene
yields were obtained in the IL (46%/other monoalkylbenzene
isomers) than with the conventional HF process. The linearity of
the alkylbenzenes is indeed an important parameter for the
biodegradability of the compounds.
One of the points of interest of operating the reaction in ILs is
that alkylbenzenes are poorly miscible in ILs. The reaction
proceeds in a biphasic mode, thus making catalyst recovery and
recycling easier. In traditional processes, consecutive polyalkylation reactions may occur since the alkylated benzene hydrocarbons are more reactive than the monoalkylated starting
material. In the biphasic IL mode, consecutive polyalkylation
reactions are disfavoured since the alkylated benzenes are less
soluble in the catalytic phase than the monoalkylated benzenes.
Analogous ILs were also evaluated supported on solids like silica
alumina or zirconia with improved activity and selectivity for
monoalkylated products [333]. This reaction has also been
performed using protic ionic liquids that are free of Lewis acidity,
such as [BMI][HSO4]/H2SO4. The difculty in that case is to nd the
right acidity level to prevent isomerisation of the olen double
bond.
6.1.2.2. Ethylbenzene production. Chloroaluminate ionic liquids
were also investigated by BP as liquid acid catalyst for the
alkylation of benzene with ethylene to produce ethylbenzene
[383]. The manufacture of this bulk chemical compound is
industrially dominated by the use of AlCl3-red oil as the acid

catalyst (red oil is dened as a mixture of AlCl3 with polyalkylate
such as diethylbenzene). It has been proven that the liquid red oil
forms a biphasic mixture with the reaction products. Unfortunately, during reaction some of the AlCl3 is gradually lost in the
reaction product which rapidly renders the system monophasic
and makes the catalyst recycling very complicated and not
economically viable. The search for biphasic alternatives led to
the use of chloroaluminate ionic liquids based on imidazolium
cation (ex: [EMI][Cl]/AlCl3 or [HNMe3][Cl]/AlCl3 in a 1:2 molar
ratio). In a very detailed study based on bench-scale experiments
[383], BP demonstrated the potential of ILs which compared
favourably with the industrial red oil. One of the main advantages
of the IL system remains the biphasic character of the mixture
which facilitates the recycling of the catalyst by gravity separation.
However, the overall outcome of the laboratory BP evaluation is
that the high cost of producing and using ionic liquid catalyst could
only be offset if certain technical targets could be met, such as at
least equivalent or superior conversion activity and ethyl benzene
selectivity to homogeneous AlCl3, a deactivation rate < 15% per
cycle, a production cost of ionic liquid catalyst <$5000/t.
6.1.2.3. Friedel-Crafts acylation of aromatic hydrocarbons. ILs have
been largely described as catalyst-solvents or solvents to perform
acylation reactions [384]. The main advantages of using ILs is the
enhanced reaction rates, conversion and much higher selectivity.
Solvation properties of ILs, which can aid in solubilising the
reactants, can allow a reduction of the number of steps in
synthesis. The acylium cation [RCO]+ is the key intermediate in
these reactions as it is the case in conventional solvents. When
Lewis acidic ILs are used a stable complex is formed between Lewis
acid and the carbonyl oxygen of the product so that an excess of
catalyst is need to achieve complete reaction. Even if ILs have
demonstrated their benets, the main issue remains the separation
of products from the ILs and the IL recycle.
6.1.3. Alkylation of olens with isobutane: IL as solvent
and acid catalyst
Isobutane alkylation is one of the most important processes for
producing reformulated gasoline. Commercial alkylation plants
use either sulphuric acid or hydrogen uoride as catalyst. Both of
them suffer from some limitations when we consider productivity,
alkylate quality, safety aspects and operating costs [385,386]. The
use of solid catalyst as alternative is an interesting issue but
problems of catalysts deactivation and regeneration must be
solved before industrial application. Very early in the development
of ionic liquids in catalysis, IFP applied acidic chloroaluminates for
the alkylation of isobutane with 2-butene or ethylene [387]. It has
been demonstrated, in a continuous-ow pilot plant operation,
that [pyridine,HCl]/AlCl3 (1:2 molar ratio) IL was the best
candidate in the case of ethylene [386]. The reaction can be run
38
Table 5
Ionikylation pilot plant alkylate vs HF and H2SO4 processesa.
Yield (wt%)
Process
HF
H2SO4
C5
C6
C7
C8
C9+
0.6
1.0
2.0
95.6
0.8
2.5
1.9
2.9
90.1
2.6
8.8
4.9
3.9
80.7
5.7
C8 components
TMPs
2,2,3-TMP
2,2,4-TMP
2,3,3-TMP
2,3,4-TMP
89.6
0.1
51.6
18.1
19.8
80.9
1.6
49.7
10.8
18.8
71.6
2.3
31.1
19.8
18.4
6.0
1.3
3.4
1.3
0
9.2
9.0
14.9
100.1
95.0
8.8
97.3
95.2
8.0
97.6
94.4
Ionikylation
DMHs
2,3-DMH
2,4-DMH
2,5-DMH
3,4-DMH
TMP:DMH ratio
RON
MON
a
that the addition of cuprous chloride enhances the acidity of the IL

and when used for alkylation reaction inhibits undesirable side
reactions such as isomerisation and cracking. Petrochina demonstrated the high stability of this catalyst through an 8-month
ageing test before a 60-day pilot scale operation. The alkylation
reaction is performed at 15 8C and 0.4 MPa. During the pilot test
period, olen conversion was more than 99%. The C8 yield in
alkylate gasoline was higher than 95% and the yield of TMP was
90% (Table 5). It is interesting to note that the non corrosive nature
of the IL-catalyst allows for the use of less costly material for the
design of the pilot (carbon steel reactors, piping, tanks, pumps and
valves). Petrochina announced in 2006 that an alkylation process
has been retrotted into an existing 65,000-tonne/year H2SO4
alkylation unit in China. Alkylation from the ionikylation process
compares favourably to alkylate from H2SO4 (Table 6). Improvements in terms of alkylate yield, process unit capacity and so
economics were demonstrated.
6.1.4. Chlorination and uorination reactions
Reproduced from ref. [389].
at room temperature and provides good quality alkylate (2,3dimethylbutane is the major product) over a period of 300 h
(MON = 9094; MON = 98101). When butenes are used instead of
ethylene, a lower temperature and a ne tuning of the ILs acidity
are required to avoid cracking reactions and heavy by-product
formation. The continuous butene alkylation has been performed
for more than 500 h with no loss of activity and stable selectivity
(8090% isooctanes are obtained containing more than 90%
trimethylpentanes TMP; MON = 9095; RON = 9598). At that
time, it had been demonstrated that the addition of copper(I)chloride to the acidic chloroaluminate improves the reaction
performance [388]. Some years later, Petrochina developed a
process called Ionikylation for the alkylation reaction [389]. The
ionic liquid used consists of a mixture of a conventional
chloroaluminate-IL with CuCl. In this composite IL, large quantities
of mixed anion like AlCl4CuCl were detected [390]. It is theorised
6.1.4.1. Chlorination. For safety reasons, the substitution of

phosgene for industrial chlorination is a subject of major concern.
In 2005, BASF reported the chlorination of diols (ex: 1,4butanediol, Scheme 50) using HCl as the chlorinated agent in
combination with an IL [391]. Compared with direct chlorination
of diol with HCl, the IL system produces almost pure 1,4dichlorobutane (98% selectivity). The presence of IL in the reaction
mixture seems to improve the HCl reactivity. Furthermore, while
the reaction proceeds, the initial homogeneous single phase
system (butanediol completely soluble in the IL) evolves through
a biphasic mixture with the 1,4-dichlorobutane in the upper
phase. The product as well as the chlorinating IL phase can be
separated off and recycled.
6.1.4.2. The liquid-phase HF uorination: IL as catalyst. Chlorouorocarbons which are still used as refrigerants in the air-conditioning
and refrigeration industry will have to be replaced by chloride-free
hydrouorocarbons (HFCs). These HFCs can be produced by reaction
of chlorinated hydrocarbons with HF through an acid catalysed
reaction. The acid catalysts usually used for this chlorine/uorine
Table 6
Alkylate from commercial H2SO4 unit before and after retrota.
H2SO4 alkylation
Ionikylation
Flow rate (tpd)
Yield (wt%)
Flow rate (tpd)
Yield (wt%)
Feed
C4
180
248
Product
Light alkylate
Heavy alkylate
Gas
Loss
Total
125.9
10.8
41.7
1.4
180
70.0
6.0
23.2
0.8
100
186.1
8.2
53.7
248
75.0
3.3
21.7
100
RON
MON
AntiKnock index
95.0
93.0
94.0
98.8
93.1
96.0
Initial boiling point

10%
50%
90%
Final boiling point
45.0
77.0
101.5
108.5
132.0
45.5
81.5
101.0
108.0
154.0
0.9
Pass
1
1.6
Pass
1
Octane rating
Distillation (8C)
Actual gum (mg/100 mL)

Doctor test
Copper corrosion at 50 8C,3 h, grade
a
Reproduced from ref. [389].
39
Scheme 50. Chlorination of 1,4-butanediol.
Scheme 51. Demethylation of 4-methoxyphenylbutyric acid.
Scheme 52. Synthesis of alkoxyphenylphosphines.
substitution are super acids based on antimony Lewis acid, such as

SbX5 (X = F or Cl) associated with Brnsted acids. However, these
catalytic systems suffer from a reductive deactivation with formation of Sb(III) species. In industrial processes, this drawback can be
overcome by the addition of Cl2 in order to re-oxidize Sb(III), but this
leads to a signicant reduction of the yield in the desired products
due to back chlorination of the uorinated products. Arkema has
demonstrated at a pilot stage that ILs based on [SbF6] anion can be
used as liquid catalyst phase in presence of HF [392]. Formation of
heteropolyanions were identied by both Raman spectroscopy and
19
F NMR. The pilot reaction has been running for more than 400 h for
the liquid uorination of trichloroethylene, exceeding selectivities of
99.5% to 1,2-dichloro-2,2-diuoroethane and 1-chloro-2,2,2-triuoroethane, without any noticeable deactivation.
6.1.5. Ether cleavage
In 2004, Eli Lilly company reported the use of pyridinium
hydrochloride [PyrH][Cl] for the demethylation of 4-methoxyphenylbutyric acid (Scheme 51), a key feedstock for the synthesis of a
medicine (LY518674) [393]. For preclinical evaluation, kilogram
quantities of this compound are required. The classical approaches
for demethylation reaction (BBr3, BBr3/Me2S, BCl3 and many others),
were not envisioned, each of them presenting undesirable features.
Eli Lilly researchers turned rapidly to the use of the melted
pyridinium hydrochloride, earlier reported for similar transformations [393]. For preventing solidication of the high melting
pyridinium hydrochloride (mp = 153 8C) during the post reaction

steps, a stoichiometric amount of HCl and dilution with water were
necessary. This way, a homogeneous non viscous catalytic solution
was obtained at room temperature with no indication of any
thermal hazards. Following the reaction, the products are
extracted from the reaction mixture by solvent extraction. This
chemistry was implemented to a 190 L scale, affording 4methoxyphenylbutyric acid in high yield and purity.
6.1.6. Acid scavenging
Alkoxyphenylphosphines are known as important raw materials for the manufacture of substances that are used as photoinitiators (BASFs Lucirines1). These alkoxyphenylphosphines are
commonly produced by reaction of chlorophenylphosphines with
alcohols. This reaction generates stoichiometric amounts of HCl
which must be trapped using a tertiary amine (Scheme 52).
Unfortunately, the corresponding ammonium salts [HNR3][Cl]
appear as a slurry, generating complicated work-up and signicantly lowering the yield and capacity of the process.
In 2003, BASF announced the development of a new process
called BASILTM (Basic Acid Scavenging utilising Ionic Liquids) to
improve the acid trapping in a more convenient way [394,395]. It
was found that substitution of the classical tertiary amine by the
liquid 1-methylimidazole reaches the stage of 1-methyl-imidazolium chloride [MI][Cl] production, a salt which remains liquid
under the reaction conditions (Scheme 53). More, this ionic liquid
Scheme 53. Alkoxyphenylphosphines synthesisThe BasilTM route.
40
Scheme 54. Hydrosilylation of C5

5C double bond with Si-H-functional polydimethylsiloxanes.
forms a second lower phase with the pure product in the upper one
giving feasible the separation of products by simple decantation
[396398]. Interestingly, the 1-methyl-imidazolium chloride
[MI][Cl] co-produced in the reaction can be treated with caustic
soda to regenerate 1-methylimidazole.
In this work, 1-methylimidazole was also identied as a
nucleophilic catalyst. When used, it led to consirable improvement
of the phosphorylation rate. Taking this effect into account, BASF
developed a specic reactor technology (jet reactor) which
increases productivity by a factor of 80,000. The role of 1methylimidazole as acid scavenging was further extended to other
similar problems and revealed to be also very efcient [365]. The
BASILTM process is actually applied by BASF at a multi-ton scale.
6.1.7. Hydrosilylation: IL as solvent and nanoparticle stabiliser
Organomodied siloxanes account for approximately 15% of the
entire silicone market and are accessible in a number of ways
[399], including the catalysed hydrosilylation of C5
5C double bond
containing compounds with Si-H-functional polydimethylsiloxanes (Scheme 54). Particularly interesting are polyethersiloxanes,
constituting an important class of surface-active compounds
which nd use in a broad range of industrial applications.
The hydrosilylation reaction is usually performed in a singlephase homogeneous system with, nevertheless the recurrent
problem of catalyst and product separation after completion of
the reaction. To overcome this limitation, Degussa introduced the
use of ionic liquid as a way of catalyst heterogenisation
[331,400,401]. This work was directed by the need for using the
standard platinum catalyst without modication. Several ionic and
neutral catalysts as well as ionic liquids were then evaluated. As an
important parameter of the study the separation behaviour of the
ionic liquid and the product were particularly studied. It turned out
that for successful recovery of the catalyst and its reusability it is
crucial to nd an appropriate combination of a catalyst and an ionic
liquid which has to be harmonised with the hydrophilicity/hydrophobicity of the product. For example of this ne tuning, it was
demonstrated that hydrosilylation with ILs derived from 1,3dialkylimidazolium salts did not give the desired polyethersiloxanes. The authors assumed that formation of NHC-carbenes which
coordinate to the Pt centre is responsible of the catalyst deactivation.
One year after this proof-of-concept, a more detailed study on this

reaction was performed with a view to nding a superior catalyst/
ionic liquid system active and stable enough for industrial
implementation [330]. Depending on the catalyst precursors and
reaction conditions, homogeneous or soluble nanoparticle catalysts
were identied as the active species. Despite the large screening
conducted in this study, none of the catalyst combinations tested
resulted in a superior catalytic system.
6.1.8. Isomerisation: IL as a solvent
Isomerisation of 3,4-epoxybut-1-ene to 2,5-dihydrofuran is
described in literature as a reaction step involved in the production
of tetrahydrofuran, a valuable compound useful as a chemical
process solvent, and as an intermediate in the preparation of
polymers such as poly(tetramethyleneether)glycol. This isomerisation process requires simultaneous activation by a Lewis base
and by Lewis acid being an organotin compounds. The Eastman
Chemical Company performed this reaction at an industrial scale
using phosphonium iodide ionic liquid (Scheme 55). This ionic
liquid was chosen for its high thermal stability, its high
hydrophobic character, as well as its limited cost with respect
to ammonium analogues. Advantages provided by this process also
include milder reaction conditions, simplied product separation
and the ability to remove and replenish the catalyst system. The
phosphonium-based IL is highly alkane soluble and can dissolve
the oligomer by-products. The 2,5-dihydrofurane (bp = 66 8C) and
the crotonaldehyde (bp = 104 8C) can then be separated from the
reaction mixture by distillation due to their low boiling points,
while the higher boiling oligomers remain in the IL-catalyst phase.
This phase is further treated with an extractant solvent such as
naphta, to recover the oligomers and recycle the IL-catalyst. In this
case, the IL is multi-task: solvent, catalyst and by-product
extractant. The industrial plant was operated from 1996 to 2004
with a reactor capacity of 1400 metric tons per year. It actually
represents the largest industrial application involving ionic
liquids.[402,403].
6.1.9. Methanol carbonylation
Industrial processes of methanol carbonylation are currently
performed in liquid phase using homogeneous catalyst systems
Scheme 55. Isomerisation of 3,4-epoxybut-1-ene to 2,5-dihydrofuran.
41
Table 7
Other examples of industrial/pilot scale applications of ILs.
Company
Scale
Ionic liquid
Role of the IL
Ref.
BASF
Pilot
[RMI][BF4]
[406,407]
Air products
Commercial
[RMI][BF4] [RMI][Cu2Cl3]
[RMI][Cu2Br3]
Entrainer for breaking

azeotropes
Liquid support
Scionix
Scionix
Pilot (1200 L)
Pilot (50 L)
[HO(CH2)2NMe3][Cl]
Electrolyte
Electrolyte
[410]
[79,125]
G24i
Commercial
Electrolyte
[411,412]
Engineering uids
Hydraulic liquids
Cleaning uids
Linde
Iolitec/Wandres
Pilot
Pilot
Liquid piston
Cleaning agent
[413415]
[365]
Analytical chemistry
Commercial GC-stationary phase
Supelco
Commercial
[1,9-di (3-vinyl-imidazolium)
nonane] [NTf2]
GC-stationary phase
[416]
Separation/storage
EtOH/H2O or EtOH/THF separation
Storage of gases
Electrochemistry
Electroplating of Cr
Electropolishing of stainless steel
Energy
Dye Sensitized Solar Cells
(DSSCs or Gratzel cells)
which are most commonly based on rhodium metal. In these

processes, the precipitation of rhodium during the ashing step
is a serious problem. Ionic liquids have been described as
solvents of the anionic active rhodium species [Rh(CO)2I2]
allowing catalyst stabilisation and recycling [404]. A continuous
process, operated in gas phase, for the production of acetic acid
from methanol and methyl iodide has also been proposed using a
non-volatile catalyst phase composed of rhodium and an ionic
liquid. As the reaction products are separated in the vapour
phase, this process simplies product purication while providing high reaction rate and eliminating the addition of water to
the reactant stream [405].
6.1.10. Other examples
Taking into account the scope of this review, we did
not develop industrial/pilot scale applications of ionic liquids
in elds other than catalysis. However, it seems that very
attractive work is actually done for using ionic liquids as
electrolytes for electroplating, as hydraulic or cleaning uids, or
entrainers for breaking azeotropes. Some of these examples are
listed in Table 7 with references to the more representative
work.
6.2. Main process engineering challenges and issues
As reported in the selected examples previously cited, it is now
obvious that ILs can contribute some signicant improvements to
various existing catalytic processes. However, to be applied in an
industrial process, ILs must meet a certain number of requirements. Changing an established industrial process for a novel
technology using ILs is not easy even if it can be more protable in
the long term. It requires a willingness to accept the risk associated
with the implementation of new approaches and products. New
environmental regulations and competition may force industry to
take the plunge. The novelty and the price/production cost of ILs
are probably one of the main barriers. The IL price must be related
to the process performance and to overall economy. So the major
issues are IL life times e.g. their chemical and thermal stability,
their loss in the process, their recovery and recycling. The novelty
of ILs raises a certain number of questions such as their toxicity,
their reliable supply, their material compatibility and their
notication requirements (REACH). Their reliable supply is today
no more a major concern as IL production and commercialisation
are developed and have attracted the development of new
companies or business.
[408,409]
6.2.1. IL stability, lifetime and recyclability

Most often, ILs display high thermal stability, the latter being
mostly dependent on the nucleophilic character of the anion.
However, very often valuable information is missing concerning
the long-term stability of ILs. In some cases, TGA analysis provides
these data but the decomposition products are often not described.
It has to be emphasised that the thermal and chemical stability of
ILs depend also on the presence of impurities from their synthesis
and on their exposure to the process conditions, reactants and
products. A typical example is the decomposition of N,Ndialkylimidazolium cation to form N-heterocyclic carbenes under
basic conditions, or the hydrolysis of [PF6] based ILs into HF and
POF3. In multiphase liquidliquid systems, pre-treatment of
feedstocks can be an important pre-requisite to protect the
catalytic system from polar impurities that can accumulate in the
IL phase. For example in the Difasol stand alone process, the
lower the content of feedstock pollutants, the longer the
chloroaluminate ionic liquid lifetime will be. The best arrangement, to remove these poisons as thoroughly as possible, includes a
water wash with condensed or feed boiling water, followed by a
water removal device. The dry feed is then treated by the proper
molecular sieves in order to remove both oxygenates and sulfur
compounds. It should be noted that all these feedstock treatments
are also recommended to minimize classical DimersolTM catalyst
consumption, but using standalone DifasolTM would lead to more
severe treatments and therefore higher investments and chemical
expenses.
In multiphase processes, it is often reported that the reaction
products are simply separated from the IL catalytic phase by
simple decantation which allows IL recycling. However, the partial
miscibility of ILs in organic reaction products, even at the trace
level, can be at the origin of IL loss and product contaminations,
which can be dramatic issues for the overall economy of the
process and product quality. To improve the product-IL phase
separation, different techniques have been envisaged such as the
use of an organic co-solvent, which can also be the non converted
recycled reactants when they are non polar (e.g. hydroformylation), or scCO2 but this renders the process scheme more complex
and more energy consuming, and could probably be proposed only
in sufciently high valuable chemical production.
Supported IL processes, that use less IL immobilized on solid
supports, could be applied in some dedicated cases. However,
these processes t best with gasliquid multiphase technology and
their applicability remains limited to reactions involving low
volatile reactants and products.
42
Scheme 56. Different possible routes to recover ILs.
Membrane separation technology could be used in the case of

separation of non volatile products that are not suitable for
distillation or phase separation. However one must consider the
typically higher viscosity of ILs, and the treatment of membranes for
IL recovery. Despite these limitations, a series of organic-solventstable nanoltration membranes have been employed to recover ILs
in Suzuki cross-coupling reaction mixtures [417]. The recovery of
hydrophilic ILs from aqueous solutions is still challenging [84].
The controlled decomposition of ILs has been proposed for IL
recycling (Scheme 56) [365]. This approach consists in transforming the IL into neutral molecules which can be recovered by
distillation. For example, protic ILs can be switched to the neutral
amine or imidazole in the presence of a base. In the case of N,Ndialkylimidazolium, the alkylimidazole can be formed by heating,
or relatively stable carbenes can be generated in presence of a base.
The distillation of ILs, without decomposition, has also been
reported [47]. But this distillation requires high temperature under
vacuum and is not realistic for large scale IL recovery.
6.2.2. Safety and environmental issues:
ILs have been claimed as being green solvents and possible
alternative to volatile organic solvents. This has been justied in
some applications where ILs, because of their negligible vapour
pressure and non-ammability, are used favourably instead of
chlorinated solvents. An example is given by the development of an
optimised process for degreasing and/or scouring metal, ceramic,
glass, plastic composite material or semiconductor surface, by
treatment of the surfaces in a solution comprising an IL [418].
Some ILs have been the subject of toxicity and ecotoxicity studies
[419] and data are now available on a larger variety of organisms
(bacteria, fungi, sh, algae.). Most studies have been carried out on
imidazolium- and pyridinium-based ILs, with alkyl or alkoxy side
chains. The variety of anions studied is limited mainly to bromide,
chloride, hexauorophosphate and tetrauoroborate. Much less
research has been devoted to the determination of the biodegradability of ILs but the design of biodegradable ILs has been covered
in recent papers [420]. A high throughput screen based on the Agar
Diffusion method was recently applied to test, in a rst rapid
approach, the toxicity of ILs towards microorganisms and to
distinguish toxic and biocompatible ILs [421].
Registration of ILs in inventories like EINECS are still rare. It is
established that side chains on the imidazolium cations have a
stronger inuence on IL toxicity. The longer and the more branched
the side chain, the more toxic is the IL. Effects of anions are
generally more complicated.
In evaluating a process (eco-efciency evaluation), not only
economics but also sustainability must be considered. Sustainability concerns the whole process from the raw materials, the
catalytic system, their manufacture, storage, transport, transformation, separation and purication of the nal products as well as
the by-products and disposal of waste. In this context, the whole

life cycle of ILs must be taken into account [422,423]. Disposal of
ILs is the main concern and is generally not reported. Disposal of ILs
by incineration can be applied.
7. ILs application in the biomass transformation into
fuel and chemicals
With the declining fossil fuel resources, combined with the
greater demand for petroleum in emerging economies, the
demographic increase and the environmental concerns, the
transition to alternative energies, such as bio-fuels, is taking place
in many countries. Discussions on current methods and future
possibilities to transform the biomass into transportation fuels and
value-added chemicals have recently emerged [424429]. Up to
now, most attention has been focused on the transformation of
vegetable oils. But with the limited amount of triglycerides
available together with ethical reasons, lignocellulosic materials,
rapidly appeared as one of the most interesting carbon neutral,
renewable, cheap and abundant resource. For example, utilisation
of wood-based biomass, mostly agricultural waste, attracted
considerable interest as an important source of glucose. This
material also has the advantage of being far less expensive than
other feedstocks (oil, corn, gas.). In a modern bio-renery, one can
expect that lignocellulose would be converted through a number of
different processes into mixture of products, including bio-fuels,
valuable chemicals, heat and electricity. The biomass transformations often use bio-chemical technologies such as fermentation or
enzymatic procedures. Biological transformations account for
main paths to convert feedstocks to building blocks. Chemical
transformations predominate for the conversion of these building
blocks to molecular derivatives and intermediates. Chemical
transformations often include reduction, hydrogenation, and
selective dehydration (acid-catalysed) reactions. The potential of
catalysis in this area is important to progress towards more
environmentally processes or to achieve more efcient and
selective synthesis under moderate operating conditions. Catalyst
development with improved stability and better tolerance to
biomass impurities would be necessary. However, the transformation of carbohydrates is still challenging task because of their low
solubilities in almost any solvent. Compared to common organic
solvents used in carbohydrate chemistry, such as LiCl/DMAc
(dimethylacetamide), ILs display interesting properties and
different reviews describe a number of their advantages to cite
just a few their reasonable chemical inertness, their rather good
thermal stability, their low volatility, their unique solvation
abilities [8]. It can also be noted that the heterocyclic-based ILs
present cytotoxicities comparable to those of many classic solvents
despite many quaternary nitrogen compounds have antibacterial
properties [430]. So, ILs open a window of opportunities for the
43
Fig. 20. The cellulose network (A: Cellulose chain and B: inter and intra H-bonds present in cellulose).
dissolution of carbohydrates (Table 9), their recovery from

solution, or their transformation into important derivatives,
particularly esters and ethers. The evaluation of the potentials
and drawbacks of the use of ILs in bio-polymer industry has been
briey evaluated [431]. One interesting point to note is their low
volatility which permits distillation of the volatile substances,
thereby making IL recovery feasible. Their power to dissolve large
concentrations of saccharides and carbohydrate polymers are now
well-known and many papers discuss the design and optimal
conditions for dissolving every type of cellulose and lignocellulosic
material. Concentrations up to 25 (wt%) of cellulose in imidazolium
type ionic liquids were found. This ability to solubilise cellulose is
useful for acid/base catalytic reactions in homogeneous solutions
directly in the ILs or for direct enzymatic hydrolysis. Finally, they
can potentially be used as alternative solvents for sugar
transformations into potential bio-fuels or bio-fuel intermediates
and for bio-transformations such as derivation of sugars or
transesterication of triglycerides. All these advantages make ILs
play an increasing role in the research and development of new
technologies in the biomass area.
7.1. Processing of lignocellulosic and cellulosic materials
7.1.1. Direct solvent for dissolution of cellulose and sugars
Cellulose consists of b-(1 ! 4)-linked glucose repeating units
(Fig. 20), it is the most abundant polymer on earth. It has been one
of the largest renewable biological resources (global volume of
cellulose is 700,000 billion tons, only 0.1 billion tons are used as
feedstock for processing of the 40 billion tons that nature
renewed), being used in industrial domains such as paper, bres,
polymers, textile, food. Natural cellulose is a highly crystalloid,
containing strong intra and inter H-bonds and van der Waals
interactions between the cellulose brils. It is insoluble in water
but soluble in concentrated phosphoric acid, insoluble in conventional organic solvents, which is the main obstacle to the more
extensive development of its use. The research for new solvents,
including ILs and phosphoric acid [432], for dissolving and
processing cellulose have attracted increasing attention. These
treatments contribute to converting crystalline cellulose into
amorphous cellulose which can be practically hydrolysed or
transformed much faster. The pre-treatment of cellulosic materials

can affect its physical properties such as its degree of polymerization, its crystallinity and even the surface area of the substrate
accessible in the case a further enzymatic hydrolysis.
For this purpose cellulose solvents should have most of the
following features [433]: (i) able to dissolve cellulose (and wet
cellulose) at low temperature: the IL ideally displays high
dissolution capacity (>10 wt% of cellulose), melting point lower
than 20 8C and high decomposition point (>200 8C); (ii) non
volatile, non toxic and chemically stable, (iii) no cellulose
decomposition, (iv) easy cellulose regeneration (e.g. with water)
and good bre properties (at least as good as viscose process), (v)
recyclable, (vi) cost effective and easy process an (vii) non toxic to
enzymatic and microbial fermentation.
The typical commonly used solvents to dissolve cellulose, over
the past decades, were based on polar organic solvents such as
DMF, DMAc, DMI or DMSO often added with charged compounds
such as [NBu4][F] or LiCl (Table 8). For example, NMMO is used as
one alternative to the carbon disulde, sodium hydroxide and
sulphuric acid in the bre production (old viscose process). It can
produce solutions of cellulose of 1015 wt% concentrations.
However, these solvents suffer from their toxicity, high cost,
dissolving capacity, difcult recycling and their thermal instability
in process conditions [39]. Consequently, processing cellulose is
often complex and in many cases more expensive than comparable
synthetically-manufactured products such as polyester bres.
Table 8
Main solvent systems used in manufacturing cellulose and cellulose derivatives
[434].
Acronym
Main systems used to dissolve cellulose
DMSO/TBAF
LiCl/DMAc
LiCl/DMI
LiCl/NMP
N2O4/DMF
DMSO/CH2O
NMMO
Dimethyl sulfoxide/tetrabutylammonium uoride

Lithium chloride/dimethylacetamide
Lithium chloride/dimethylimidazolidinone
Lithium chloride/N-methyl pyrrolidine
Dinitrogen tetraoxide/dimethylformamide
Dimethyl sulfoxide/paraformaldehyde
N-methylmorpholine-N-oxide monohydrate
Aqueous solutions metal complexes
44
The rst report of dissolution of cellulose in an IL dates back

from a US patent led in 1934. The ionic solvent used was the [Nethylpyridinium][Cl] in a presence of a nitrogen base such as
pyridine but this system displayed a relatively high melting point
(mp: 118120 8C) [435]. In 2002, Rogers et al. report that cellulose
could be dissolved in ionic liquids [436]. They used several ILs,
cellulose and operating conditions and concluded that the best
cases, with concentrations of cellulose in the 812 wt% range and
up to 25 wt% by microwave activation, were found with 1-butyl-3ethylimidazolium chloride (BMIC) as the solvent. But it can be
noted that degradation under microwave irradiation seems to be
higher than under conventional heating conditions [437]. These

results opened up a new way of developing a class of cellulose
solvent systems and initiating an extensive research in this area.
Overall, the ability of ILs to dissolve cellulose depends on the
nature of the native cellulose (its degree of polymerization DP, and
its crystallinity) on the operating conditions (temperature,
reaction time, initial concentration of cellulose in the IL, activation
with microwaves) and presence of impurities, mostly water that
can signicantly change the result. Indeed, the use of non-dried ILs
can affect the solubility of cellulose and it was demonstrated that
severely dried ILs are indispensable for an optimal dissolution
Table 9
Examples of solubility of different bio-products in ILs and organic solvents.
Solvent
Solubility
Glucose
substrate
DP (cellulose)
2-Methyl-2-propanol
[BMI][N(CN)2]
[BMI][Cl]
0.03 (wt%)
145 (g/L)
50 (g/L)
Sucrose
Sucrose
Sucrose
Sucrose
Sucrose
Acetone
Pyridine
[BMI][Cl]
[BMI][Cl]
[BMMI][Cl]
[BMI][Cl]
[BMI][Cl]
[BMI][Cl]
[BMI][Cl]
[BMI][Cl]
[BMI][Cl]
[BMI][Cl]
Cellulose
Cellulose
Cellulose
Cellulose
Cellulose
Cellulose
Cellulose
286
593
1000
1000
1000
1198
6500
Cellulose
225
Cellulose
T (8C)
Ref.
25
25
70
[444]
[444]
[445]
0.007 (wt%)
6.45 (wt%)
5 (wt%)
18 (wt%)
14 (wt%)
30
26
70
110
120
[430]
[430]
[445]
[446]
[446]
18
13
3
10
25
10
6
83
83
70
100
110
83
80
[447]
[447]
[436]
[436]
[436]
[447]
[448]
(wt%)
(wt%)
(wt%)
(wt%)
(wt%)a
(wt%)
(wt%)
[BMI][Fm]
8 (wt%)
110
[441]
250
286
593
1198
[BMMI][Cl]
[BMI][Cl]
[BMI][Cl]
[BMI][Cl]
4.5 (wt %)
9 (wt%)
6 (wt%)
4 (wt%)
110
80
80
80
[446]
[449]
[449]
[449]
Cellulose
650
1600
[AMI][Cl]
[AMI][Cl]
14.5 (wt%)
8 (wt%)
80
80
[450]
[451]
Cellulose
286
593
1198
[AMMI][Br]
[AMMI][Br]
[AMMI][Br]
12 (wt%)
4 (wt%)
4 (wt%)
80
80
80
[449]
[449]
[449]
Cellulose
250
250
[AMI][Fm]
[AMI][Fm]
10 (wt%)
22 (wt%)
60
85
[77]
[77]
Cellulose
286
593
1198
[EMI][Cl]
[EMI][Cl]
[EMI][Cl]
12 (wt %)
6 (wt %)
4 (wt%)
80
80
80
[449]
[449]
[449]
Cellulose
Cellulose
Cellulose
Cellulose
Cellulose
Cellulose
795
200250
200250
200250
200250
200250
[EMI][Ac]
[EMI][PO2(H)(OMe)]
[EMI][PO2(Me)(OMe)]
[EMI][PO2(OMe)2]
[EMI][PO2(OEt)2]
[MMI][PO2(OMe)2]
20
10
10
10
14
10
80
45
55
65
100
100
[439]
[451]
[451]
[451]
[437]
[437]
Cellulose
286
593
1198
[BMPy][Cl]
[BMPy][Cl]
[BMPy][Cl]
39 (wt%)
37 (wt %)
12 (wt %)
105
105
105
[447]
[447]
[447]
Cellulose
200250
6.8 (wt%)
70
[452]
9.7 (wt%)
13.9 (g/L)
110
75
[446]
[453]
50
50
[453]
[453]
130
[454]
85
85
85
85
[455]
[455]
[455]
[455]
80
[456]
[(HO(CH2)2)MI][Cl]
(wt%)
(wt%)
(wt%)
(wt%)
(wt%)
(wt%)
Lignin
[BMI][Cl]
[BMI][Cl]
Lignin
Lignin
[MMI][MeSO4]
[BMI][MeSO4]
Wood keratin bres
[BMI][Cl]
11 (wt%)
[EMI][Ac]
[EMI][Cl]
[BMI][Ac]
[BMI][Cl]
13.5
15.8
13.2
13.6
[BMI][N(CN)2]
15 (wt%)
Eucalyptus
Eucalyptus
Eucalyptus
Eucalyptus
pulp
pulp
pulp
pulp
Starch
a
Microwaves heating.
569
569
569
569
344 (g/L)
312 (g/L)
(wt%)
(wt%)
(wt%)
(wt%)
[437]. The main results on cellulose dissolution in ILs are

summarised in Table 9. Today more than 20 ILs are known for
dissolving cellulose and are compared in terms of their dissolution
kinetics in a study [438]. A screening of different cations and
anions was also undertaken by different groups [439] and recently
some reviews on the cellulose solubilisation in ILs have appeared
[39,430,431,440443].
7.1.1.1. Anion effect in the dissolution. To dissolve carbohydrates, a
large number of ILs with different anions were screened. Rapidly
[BF4] and [PF6] anions were eliminated due to their poor
capability to dissolve any kind of cellulose [457]. For the same
reason [NTf2] and [N(CN)2] based ILs were rejected [441], also
[N(CN)2] are known as an enzyme denaturing anion. As presented
in Table 9 good dissolutions of cellulose may be obtained using
halide based-ILs, especially with the chloride anion. It is well
known that the higher the anion concentration, the better the
solubilisation; thus the small size and the strong electronegativity
of the chloride are obvious advantages [458]. In addition, these ILs
are cheaper than most ILs obtained by anion-exchange reactions
using imidazolium halide salts as starting materials. However, it
was also demonstrated that the fairly high melting point of ILs
containing chloride anion (above 70 8C for [BMI][Cl]) could be a
technical drawback and possibly limit their practical application in
cellulose processing or homogeneous cellulose derivatisation [84].
Relatively high dissolution temperatures (often above 80 8C) are
often required for dissolving cellulose, which possibly results in
cellulose modication by ILs themselves [459] and in thermal
decomposition of ILs [460] and produce some organohalogenides
[461], which have uncertain toxicity and hazardousness. It should
be noted that in general, the high viscosity of the [BMI][Cl] and
high hygroscopicity of halide ILs [441] make their handling
difcult [437].
Some groups claim that we need a new class of ILs to replace
these current chloride salts, which can dissolve cellulose with
lower viscosities and melting points but with a sufcient polarity
to further process it [443]. Thus new classes of ILs were
investigated. Formate, acetate or phosphate based imidazolium
ILs have been used and showed interesting potential to dissolve
cellulose under mild conditions. ILs containing formate anions, for
example, were found to be good solvents for dissolving cellulose.
Indeed allyl-methylimidazolium formate [AMI][Fm] dissolves up
to 22% of cellulose, presenting a DP around 250, when [BMI][Cl]
shows a solubilisation around 18% with the same substrate
(Table 9). This result can be explained by the low viscosities of
these types of salts due to the small ion size [77]. However formate
ILs generally exhibit low thermal stability, especially compared to
those based on [NTf2] and [Cl], due to decarboxylation [451] and
are known to be quite basic and unsuitable for enzymes [441].
Acetate-based ILs such as [EMI][Ac] were found to be an interesting
alternative due to the lower melting point, lower viscosity and
their less toxic and corrosive character compared to chloride-based
ILs [462]. Solutions containing as high as 20 wt% of cellulose could
be obtained. In addition acetate-based ILs are more thermally
stable than formate [441] and could dissolve cellulose without gel
formation [439]. Acetate ions are considered as the choice anion by
several groups [441].
Another alternative is the use of phosphate anions. Indeed, the
ethyl-methylimidazolium
methylphosphonate
[EMI][PO2(H)(OMe)] IL allows the preparation of a 10 wt% cellulose solution
(at 45 8C for 30 min) with stirring, or to dissolve 24 wt% cellulose
without heating. Also, phosphate-based ILs present high thermal
stability in the 260290 8C range and low viscosities [451].
7.1.1.2. Cation effect in the dissolution. Although some simulation
studies [463,464] and some conclusions of several groups
45
[430,465] suggested that little or weak interaction between cation

of ILs and cellulose existed, it can be admitted that cations were
involved in the dissolution process and their role in the
dissolution mechanism should not be neglected [458,450,466].
Thus, for a same chloride anion, increasing the alkyl chain on the
dialkyl imidazolium cation leads to a decrease in cellulose
solubilisation. Introduction of a function such as an allyl group
on the imidazolium cation gave superior results, up to 14.5% of
cellulose can be dissolved using the allyl-methylimidazolium
chloride [AMI][Cl] when 13% of the same cellulose was dissolved
using the [BMI][Cl]. Allyl based ILs generally showed lower
viscosity than those having propyl or propargyl groups [77]. Also,
[AMI][Cl] can be viewed as a smaller cation because it contains
only three carbon atoms in the side chain, and the strong polar of
the double bond seems to be essential [39]. Some results indicate a
relatively high solubility of avicel1 cellulose (DP = 225) in
[BMI][Fm] as high as 8 wt% when the solubility of the ammonium
formate salt [Bu4N][Fm] is only 1.5 wt% [441]. This correlates with
a cation effect such as the dissolution results obtained with a
pyridinium chloride salt compared to the corresponding [BMI][Cl]
salt [447].
7.1.1.3. Main properties involved in the dissolution process. The
main properties of ILs relevant to the dissolution and functional
modication of cellulose and carbohydrates are their polar
character (see Kamlet-Taft parameter), the basicity of the IL
anions and their ability to generate H-bonds. For example, the
hydrogen bond basicity for the [BMI][Cl] is around 0.85 when this
value is 1.09 for the corresponding [BMI][Ac]. But the most
important contribution can be ascribed to hydrogen bonding
ability of the IL anion, such as chloride which gives H-bonding with
the hydroxyl groups of the bio-molecule (the solubility of biomaterials in [BMI][Cl] decreases after methylation of the hydroxyl
group of cyclodextrins) [467].
The ions of ILs are large and asymmetric, probably freer to
interact with OH groups of the cellulose than that of classical
chloride ions of LiCl in N,N-dimethylacetamide.
Higher concentrations of cellulose in acetate-based ILs compared to chloride-based ILs can be obtained due to the lower
viscosity of the solutions, providing promise for more efcient
processes in cellulose dissolution and shaping for bres manufacture [462].
In a typical process for dissolving cellulose, the media has to be
heated, so that in these conditions the thermal stability is also an
important aspect.
In Table 10, some melting points are considered, but this
property is highly dependent on the IL purity. For example
different values for the same IL melting point (mp) can be found in
the literature, with the [BMI][Cl] the mp is found at 41 8C for a
group [468] when 73 8C is found for another one [447].
7.1.1.4. Mechanism of dissolution. Insight into the mechanism of
dissolution of cellulose in ILs has been achieved by applying
different analytical methods. NMR spectroscopy and molecular
dynamics simulations were applied to show that ILs act as non
derivatising solvents of cellulose [447]. It was shown that the anion
of the IL acts as H-bond acceptor or electron donor centre which
interacts with the hydroxyl group of cellulose in approximately
stoichiometric manner [469,470] to form a conceptual electron
donor-electron acceptor (EDA) complex (Scheme 57) [39]. It has
been thought that the anion was the major contributor and the
cation did not play a signicant role in the dissolution. Actually the
cation, with its electron-rich aromatic p system, can be seen as an
electron acceptor centre via non-bonding or p electron interactions, and moreover can prevent the crosslinking of the cellulose
[458].
46
Table 10
Some parameters to consider regarding the solubility of bio-polymers in ILs.
IL cation
IL anion
Mp (8C)
Viscosity
mPa s (at RT)
Solvato-chromic
parameter b*
Interest/limitations for bio-polymer processing
[BMI]+
[AMI]+
[AEI]+
[AMI]+
[BMI]+
[BMI]+
[BMI]+
[BMI]+
[BMI]+
[Cl]
[Cl]
[Fm]
[Fm]
[Fm]
[NTf2]
[OTf]
[N(CN)2]
[PF6]
66
17
<20
76
11,000
2090
67
66
156
52
0.830.87
0.83
0.99
0.99
1.01
Corrosiveness of the anion; possible degradation of cellulose

Readily dissolve cellulose up to 14.5% (cotton linter)
Low viscosity, high basicity of the anion
Solubilise 10 (wt%) cellulose at 60 8C
Higher b value than chloride; but limited thermal stability
Good thermal stability/bad dissolution
[BMI]+
[Ac]
[EMI]+
[EMI]+
[EMI]+
[EMI]+
[Ac]
[PO2(H)(OMe)]
[PO2(Me)(OMe)]
[PO2(OMe)2]
[EMI]+
[MeOSO3]
[MeSO3]
[BMPy]+
[Cl]
2
13
6
0.46
0.21
<20
86
66
74
646
1.09
140
107
510
265
1.00
1.07
1.00
Less corrosive than Cl; non-toxic; but limited thermal

stability (110-120 8C) due to decarboxylation
Concentrations as high as 20 wt%
Very low viscosity
0.61
0.70
Cellulose dissolution
95
Effective dissolution of cellulose; but high melting point
b H-bond basicity, solvatochromic dye: 2,6-dichloro-4-(2,4,6-triphenyl-1-pyridinio)phenolate.
Interactions between cellulose and ILs and formation of the EDA

complexes are possible if the anion and cation are located close
enough. Then the hydrogen bonds network between the glucosidic
monomers in the cellulose are disrupted, resulting in the
solubilisation [39].
The effect of the temperature is also a non-negligible
parameter, indeed above the critical temperature, the ion pairs
in the [AMI][Cl] IL dissociated to Cl and AMI+ ions. Then free Cl
ions associated with the cellulose hydroxyl protons and free
cations complexed with cellulose hydroxyl oxygen, which led to an
easier dissolution of cellulose [443].
7.1.1.5. Precipitationregeneration. Cellulose dissolved in ILs can
be precipitated from its solution by addition of a non-solvent such
as water, ethanol or acetone. The regenerated cellulose is separated
by ltration or centrifugation and due to its non-volatility, the IL
can be recovered after elimination of the anti-solvent through
distillation. Recovery of the ILs is important for future costeffective processing of cellulosic material. Studies on biphasic
systems for recovery have been investigated using IL/water
[457,471], IL/alcohol [472], IL/supercritical CO2 [473] or two
immiscible ILs [167]. Another approach has been examined using
sugars or sugar derivatives as water-IL solution additives for
preparing two-phase media. Sucrose is added to a solution of IL in
water to separate the IL, in moderate purity, from the aqueous
phase [84,474]. But in any case the recovery of the IL is still
incomplete and needs to be improved through future research.
Regenerated cellulose could be obtained in different forms such
as monoliths, bres and lms. Compared to the native cellulose,
Scheme 57. Possible insertion of an imidazolium chloride in the cellulose matrix.
the regenerated sample can have the same degree of polymerization and polydispersity, although this much depends on the
operating conditions of the treatment. Generally macro- and
micro-structure especially the degree of crystallinity can be
drastically changed and modulated by changing the conditions
of regeneration. For example, cellulose reconstituted after being
dissolved in [AMI][Cl] and [BMI][Cl] had lower degrees of
crystallinity than native cellulose [475]. It has been shown that
the resultant regenerated cellulose is mostly amorphous with
greater accessibility of the polysaccharide chains to cellulase and
exhibits improved enzymatic hydrolysis kinetics (Fig. 21)
[458,466,476].
7.1.2. Treatment of lignocellulosic materials
Lignocellulosic biomass (Fig. 22) which comprises cellulose
(3345%), hemicellulose (2030%) and lignin (1530%) is perceived
as a future valuable resource but separation, recovery and
processing of all its components in a cost-effective way represents
a signicant technical challenge. The effectiveness of lignocellulose
pre-treatment is one of the keys to successful conversion of this
originally low-cost material into sugars and by enzymatic or
catalytic hydrolysis into biofuels or biofuel intermediates.
A number of lignocellulose pre-treatments are being investigated either at lab scale or in pilot plants, including various
chemical, physical or physico-chemical approaches such as acidbased methods (dilute or concentrated sulphuric acid), steam pretreatments (steam explosion), solvent extraction methods (organosolv) or ammonia methods (ammonia bre explosion (AFEX),
ammonia recycle percolation (ARR)) [477]. Many of these
techniques suffer from relatively low sugar yields, high costs
and fractionation and isolation of the major components remains
uncompleted. All these pre-treatments have the main objective of
separating the cellulose for a future enzymatic conversion.
However limiting factors exist and hinder the accessibility to
the enzymes. Generally these factors are divided into two groups:
the biomass structural features, the so called biomass recalcitrants,
and the enzyme mechanism. While enzymatic hydrolysis solely
depends on the accessibility, the structural feature is more
complex [478].
Recalcitrances of lignocellulosic bio-materials to cellulase
enzymatic hydrolysis can be attributed to the accessible surface
area, crystallinity, the protective lignin, degree of polymerization
47
Fig. 21. Enzymatic hydrolysis of cellulose [466].
Choosing the appropriate pre-treatment for a biomass feedstock is often a compromise between minimizing degradation of
the hemicellulose and cellulose while maximising the ease of
enzymatic hydrolysis of cellulosic substrate.
Fig. 22. lignocellulose network.
and biomass particle size [431]. Conventionally the presence of the

lignin and the cristallinity are identied as the major factors. It has
been shown that removal the lignin has an important impact in the
biomass disgestibility [479]. Also, the presence of hemicellulose at
the surface of cellulose blocking its accessibility [480].
Lignin is an amorphous poly-phenolic polymer (the second
most abundant on earth) which is co-produced during chemical
pulping under acidic or harsh basic conditions (approximately 26
million tons of lignin are produced annually, globally from wood)
[453]. Methods for removing this strong, three-dimensional,
protective and highly complex network that envelops the cellulose
bres is explored but needs several improvements.
A study demonstrated that the methylsulfate imidazoliumbased ionic liquids exhibit the best ability to dissolve softwood
kraft lignin [453] another study showed that extraction of lignin
from bagasse using the ionic liquid ethyl-methylimidazolium
alkylbenzenesulfonate [EMI][ABS] was successfully achieved at
atmospheric pressure with over 93% yield. However a number of
issues remain, such as simplication of ionic liquid and the high
temperatures (170190 8C) involved [481]. When 40% of the lignin
was extracted, with a well chosen IL ([EMI][Ac]), the cellulose
crystallinity index dropped below 45 and the resulting hydrolysis
of the wood our cellulose is measured above 90%. This study
concluded in a close correlation between lignin extraction and
residual cellulose crystallinity [475]. Finally another group
concluded that delignication alone is sufcient for effective
hydrolysis over longer periods whereas for shorter hydrolysis
times the combination of delignication and decrystallization
shows great benets [478].
The pre-treatment and eventual fractionation of lignocellulose
would permit (1) amorphous cellulose generation, (2) improved
enzyme use in the cellulose hydrolysis step with possible enzyme
recovery leading to higher sugar yield with lower sugar degradation and less inhibitor formation and (3) fractionation of
lignocellulose for better economy and possible applicability to a
diversity of biomass feedstock.
7.1.2.1. Solubilisation. Some research on the solubilisation of

lignocellulose with ILs has recently emerged [482485] but
remains less abundant than for cellulose dissolution. In these
reports it was shown that the mixture [BMI][Cl]/DMSO (85/15%)
extracts both cellulose and lignin in an approximately equal
manner [483]. Apparently, two parameters are essential for the
wood solubilisation. The rst is the wood particle size, which
involves the complex and compact structure of the wood that
inhibits the diffusion of the ILs into its interior resulting in partial
dissolution of wood chips. The second is the water content of the
wood. Thus, water was found to reduce the solubility in ILs [483].
The correlation between lignin solubilisation and wood dissolution
is not evident and some ILs can solubilise lignin without signicant
effect on wood [475]. Thus the dimethylimidazolium methylsulfate [MMI][MeSO4] dissolves >500 g of lignin per kg of IL and does
not dissolve wood.
Best solvents for lignocellulosic materials are found to be the
[BMI][Cl] and especially the [AMI][Cl] for hardwood and softwood
[438,475], also [EMI][Ac] can be used for certain type of wood
(Fig. 23) [438]. Dissolution of wood can be signicantly increased
using microwaves, thus 5 wt% of six biomass types were rapidly
and completely dissolved using microwave irradiation in [BMI][Cl]
[486].
7.1.2.2. Mechanism. As for cellulose, ILs are responsible for the
hydrogen bonding disruption of the lignocellulosic complex
matrix. This is mostly attributed to IL anions, especially the
chloride anion [438]. In the same way as cellulose, the cation can
Fig. 23. Example of wood chips dissolution in [EMI][Ac] as the ionic liquid
(reprinted from [438], Copyright 2009, with permission from Elsevier).
48
Scheme 58. Schematic lignocellulose hydrolysis.
play a non-negligible role in the solubilisation. Thus Kilpelainen

et al. suggest that pp interactions exist between the IL cation and
the aromatic compounds of lignin [482]. This hypothesis can be
conrmed by the dissolution obtained with the [AMI][Cl] IL, which
is a good solvent for every kind of wood and the only one which
exhibits p-electrons on the side-chain [438]. The possibility to
acetylate the cellulose of solubilised biomass proved that the wood
solutions are real solutions and no gel or suspensions [482].
7.1.2.3. Remaining issues. The application of ILs can provide a
potential new method of fractionation of lignocellulosic materials.
But the fractionation using ILs faces some challenges to develop a
feasible process: (i) the recovery and reuse of ILs. The cost of IL is
still high despite some development to decrease it [487,488], the
majority of ILs remain expensive. (ii) The recovery of lignin and
hemicellulose from the ILs after cellulose has been extracted. In
this way lignin, which is mainly used as combustible, would be
valued and served as new starting material for different uses such
as dispersants or emulsiers [489,490].
7.2. Applications of the use of ILs in the dissolution of
ligno-cellulosic materials
7.2.1. An improvement in the analysis of lignocellulosic material
Lignocellulosic materials have complex structures and compositions. The analysis of such materials requires a series of reactions
and separation procedures. Dissolution of lignocellulose in ILs
could make analysis simpler. High-resolution 13C NMR has been
used for determining the composition of cellulose-hemicellulose
lignin mixtures [483,491]. Complete phosphitylation of all
cellulose hydroxyls can be obtained in [AMI][Cl] and for 31P
labelling. This can be useful for understanding of the interactions
occurring in these solutions [492].
7.2.2. Transformation of poly-saccharides in sugars using ILs
7.2.2.1. Acid-catalysed hydrolysis of cellulose and lignocellulose in
ILs. Acid hydrolysis of cellulose has been known for a long time,
but this method is not yet cost-effective for large-scale applications. Several main issues have nevertheless been addressed such
as harsh conditions of temperature (>200 8C) and pressure for
diluted acid hydrolysis, formation of undesirable degradation
products that lower the glucose yield and inhibit subsequent
fermentation, requirement of corrosive resistant materials and
disposal problem for concentrated acid processes. Therefore,
hydrolysis of lignocellulose or cellulose remains a challenge
(Scheme 58). When cellulose (DP ranging from 100 to 450) is
dissolved in an IL, such as [BMI][Cl], protons added in the solution
can more easily access to the b-glucosidic bonds to perform the
hydrolysis. Therefore it seems that a physical barrier can be
overcome through the formation of the cellulose solution which
facilitates the acid-catalysed hydrolysis at relatively low temperature (100 8C) and lower catalyst loading. The strength of the acid in
the IL plays an important role with efcient hydrolysis obtained
with H2SO4, 77% of total reducing sugars (TRS) and glucose yields is
obtained with 0.11 acid/cellulose ratio at 100 8C [493].
Cellobiose was found to be a good model for determining the

efcient conditions for cellulose hydrolysis; this model was then
successfully applied to hydrolysis of more complex polysaccharides in ILs. Optimised conditions have been thus determined: a
strong acid, water content between 5 and 10% (w/w), carbohydrate
content less than 10% (w/w) and temperature between 80 and
150 8C [494]. These conditions were also tested for miscanthus
grass and did not lead to an efcient cellulose hydrolysis (less than
5%). For the lignocellulosic materials, it was proposed to combine
an extraction of the lignin, as described elsewhere [475,481], and
hydrolysis in these conditions in order to optimise yields [494].
Hydrolysis of lignocellulose from different origins was performed in [BMI][Cl] added with different Brnsted acids (Scheme
59), and in parallel, for comparative purposes, in water under
otherwise comparative conditions. The catalytic activity in
[BMI][Cl] follows the order HCl > HNO3 > H2SO4 > maleic acid>H3PO4. Depolymerization of the polysaccharides occurs quickly
except with phosphoric acid yielding up to 70% TRS, when 4% TRS
yield is obtained in water, according to the analytical method
which is solely a UV absorbance measurement [495]. Almost
complete (97% after 2 h) hydrolysis of carbohydrate content of pine
wood in [BMI][Cl] was found possible using triuoroacetic acid
(0.2 wt%) at 120 8C. But the non-selectivity (conversion of the
cellulose into monosaccharides, hydroxymethylfurfural (HMF) and
furfural) observed remaining an issue [496]. A continuous
extraction system can be envisaged to obtain higher yields because
cellulose degradation seems to be unavoidable [494].
Depolymerization/hydrolysis of cellulose over solid acids,
which is not application to conventional slurry of cellulose in
water, becomes feasible in ILs. Different solid acids (Amberlyst,
Naon, alumina, sulfonated zircona, zeolithes) have been tested
to hydrolyse either microcrystalline cellulose or a-cellulose in
[BMI][Cl]. The hydrolysis of b(1!4) glycosidic linkages is
catalysed by the acid surface sites. Especially acid resins with
large pores are found suitable for cellulose or wood depolymerization in [BMI][Cl] ionic liquid. The reaction proceeds
quite selectively (no sugar dehydration products) and forms
cello-oligomers which can further be broken into sugars
with enzymes. Since monomer sugars are completely
soluble in the IL, it seems that stopping at the oligomer stage
may be an advantage for the separation of the products by
adding water. It must be noted here that the further separation
of the IL from water is not so easy and requires energy. These
results prove that inorganic solid acids can catalyse reactions in
ILs. It seems that possible interactions between [BMI][Cl] and
material surfaces do not poison the catalytic activity. On the
contrary, [BMI][Ac], which could have been more suitable
because of its lower viscosity, led to rapid destruction of the
catalyst [497].
Scheme 59. ILs used for catalytic hydrolysis of lignocellulose.
7.2.2.2. Enzymatic transformation of carbohydrates in ILs. Since ILs

dissolving carbohydrates are typically composed of anions that
form strong H-bonds with carbohydrates, they also present the
drawback of having a strong tendency in denaturing enzymes.
Indeed, strong deactivation of cellulase was found with the widely
used [BMI][Cl] IL for cellulose hydrolysis [239].
A ne design of new ILs has been achieved that are able to
dissolve carbohydrates but do not considerably inactivate enzymes
such as lipases. The carbohydrate dissolution is made possible
thanks to the presence of oxygen-containing cation having low
bulkiness combined with hydrogen-bond forming anion. The
concentration and the nature of anions are essential for
carbohydrate stabilisation [441]. Despite a study on the quaternary
ammonium cations (such as the N,N-dimethylethanolammonium
series) with acetate as the anion that shows a high tolerance of
cellulase for these kinds of ILs [486], it was shown that a
combination of acetate anions and oxygen-containing cations
causes severe cellulase inactivation at low concentrations (2.0 and
3.0 M) [498].
Design of new ILs for enzymatic transformations should be an
important future prospect, phosphate anion could be one of them
as this anion shows high compatibility with enzymes and provides
better cellulose conversion than for the corresponding acetate
anion IL in the same conditions [499].
In conclusion, the transformation of poly-saccharides using
ILs is still limited. First, enzymatic hydrolysis suffers of low
reaction rate and enzymes remain too expensive. More, acid
hydrolysis remains difcult to control generating side products,
some of them acting as inhibitors for further bio-transformation
steps.
7.2.3. Catalytic transformation of sugars
7.2.3.1. Dehydration
of
sugars in
5-hydroxymethylfurfural
(HMF). Glucose and fructose are potential interesting renewable
building blocks for the synthesis of chemical intermediates. Recent
efforts have been devoted to convert these sugars to 5hydroxymethylfurfural, a versatile intermediate which can serve
to replace petroleum-based building blocks. However, the high
production cost of HMF actually limits its availability. The current
processes use acid catalysts, they are limited to fructose as
feedstock and they produce side reactions and by-products, such as
levullinic acid, which are difcult to separate (Scheme 60). It was
known that high yields in HMF from glucose could be obtained by
using strongly polar solvents such as DMSO, in organicaqueous
reaction media. By solubilising the sugar in well-selected
imidazolium-based ILs, it is now possible to convert glucose to
HMF with a yield near 70% with negligible amounts of levulinic
acid formation. This has been made possible thanks to the addition
of metal salts, such as CrCl2 to the chloride based IL [500]. The
possible formation of [EMI][CrCl3] was suggested. The CrCl3-anion
would play a role in proton transfer to facilitate the mutarotation
of glucose (considered as the key step), leading to the isomerisation
of glucose to fructose followed by dehydration to HMF.
49
Table 11
Results of homogeneous cellulose acetylation in ILs (acetic anhydride is used as
reagent).
Ionic liquid
Reagent mol
per glucose unit
t (min)/T (8C)
Degree of
substitution
Ref.
DMAc/LiCl
[BMI][Cl]
[EMI][Cl]
[BMMI][Cl]
[AMI][Cl]
[AMI][Cl]
[EMI][Ac]
[EMI][Ac]
5
5
3
3
5
5
3
5
120/80
120/80
120/80
120/80
15/80
480/80
15/25
15/25
12.94
2.72
3
2.92
0.94
2.49
2.31
3.00
[504]
[447]
[449]
[449]
[505]
[505]
[443]
[443]
Methylimidazolium chloride [MI][Cl] ionic liquids have also

been used both as solvents and catalysts for the dehydration of
sucrose. The absence of HMF degradation products has been
ascribed to the continuous separation of HMF with diethyl ether.
Nevertheless, it would be very difcult to transpose this
methodology to a larger scale [501].
The dehydration reaction of fructose to HMF has been ascribed
to the presence of acidic ionic liquids [502], but few studies have
been completed to illustrate the relationship between the acidities
of the ionic liquids and their activities in this reaction. It has been
suggested that the reaction performance of the dehydration
reaction of fructose to HMF is closely associated with both the
acid strength and the acid type of the catalyst. Lewis acid ILs were
found to be better reaction media than Brnsted acidic one [503].
7.2.3.2. Derivation of (poly)saccharides. The solubilisation of carbohydrates in ILs has enabled a number of chemical derivatisations
of these natural products in homogeneous solutions. The activity of
the homogeneous solutions of cellulose in ILs has been studied for
different reactions such as carboxymethylation, etherication or
esterication and used for several advantages: (i) no by-products,
(ii) ILs can be repeatedly used, (iii) control degree of substitution.
One of the most important cellulose reactions is acetylation,
with a wide range of applications for coatings, membranes or
textiles. Until now commercial cellulose acetate was produced in
heterogeneous conditions with an excess of acetic anhydrides and
in the presence of sulphuric acid and one drawback, among others,
was the high energy demand required by this procedure. Since ILs
can be a suitable solvent for cellulose, it was shown that
acetylation occurred readily in this media and a large number of
ILs were tested (Table 11). [BMI][Cl] was found to be a good
reaction media, it was thus possible to form cellulose acetate with
a degree of substitution (DS) value of 2.72 in one step procedure
[447]. The reaction can be carried out rapidly when [EMI][Ac] is
used as solvent, indeed at room temperature and in 15 min
cellulose acetate with a DS between 2.31 and 3 is obtained [443].
Complete acetylation of wood was also possible using ILs, after
an addition of a mixture of acetic anhydride and pyridine, the
reaction was characterized by disappearance of the hydroxyl
Scheme 60. Conversion of fructose to 5-hydroxymethylfurfural [500].
50
Table 12
Methanolysis of triglycerides using ILs.
Catalyst
Ionic liquid
Use
Remarks
Ref
Metal salts
[BMI][InCl4]
IL-catalyst
Catalyst deactivation; no possible recycle;

leaching of catalyst
[512]
Organic base:
NaOMe, KOH, LDA. . .
[PR4][N(CN)2]
Base immobilized in the IL
10 recycles by evaporation of MeOH, then separation

of the ester by decantation; increased reaction rate by
using ultrasounds; not compatible with the presence
of free fatty acid
[509]
Tin compound
[BMI][PF6]
Three-phase system
Separation of the product by adding water to the

reaction mixture
Leaching of the catalyst
[511]
Ester/water-glycerine/
IL-catalyst
Lewis acid
[BMI] based
chloroaluminate
IL-catalyst
Chloroaluminates are water reactive; main issue is

the separation of the product from the IL-catalyst
[515]
Brnsted acid
Sulfonated imidazolium
Acid supported on
the BMI cation
Applied to treat waste oils
[514]
Compatible with the presence of free fatty acids

Enzyme lipase
[BMI][NTf2]/water
Biphasic system
groups and appearance of strong C5

5O bands in IR [482]. The nondegradative nature of ILs and their high power to dissolve cellulose
offer an excellent platform for other reactions such as: (i)
tosylation, which is made in [AMI][Cl] and permit degrees of
substitution around 1 [506] (ii) tritylation of cellulose in
[EMI][Et2PO4] [437] (iii) esterication using fatty acid chloride
leading to cellulose laurates with DS from 0.34 to 1.54 [449], (iv)
etherication for making carboxymethyl cellulose with DS of 0.49
in [BMI][Cl] mixed with DMSO as a solvent and NaOH as a base
[447], (v) encapsulation of biomolecules such as heparin on solid
support or the synthesis of polymeric derivatives composed of insitu polymerizable ILs and cellulose [507].
7.3. Transformation of vegetable oils
7.3.1. Transesterication of triglycerides: biodiesel production
Biodiesel is a C16C18 fatty acid methyl ester which can be
blended with conventional diesel to provide an alternative to the
latter [508]. Total EU27 biodiesel production for 2007 was over 5.7
million metric tonnes, a 16.8% increase relative to 2006 gures.
Biodiesel is produced by transesterication of vegetable oils,
animal fats, or even recycled greases with methanol, and glycerol is
formed as a co-product. Current processes mainly employ
transesterication of triglycerides with methanol using NaOH or
NaOMe or KOH as a base catalyst. The main drawback of this
process is the formation of soaps, which lead to separation
difculties, and the great amount of salt and waste water
produced. Acid catalysed homogeneous transesterication is
penalized by the need of higher temperature and methanol-tooil ratio as well as the formation of by-product. To overcome these
problems several alternative approaches have been developed
such as heterogeneous catalysts. Enzymatic systems or the use of
supercritical methanol are also currently under investigation but
are disfavoured by high cost.
Several authors have used the versatile solvent properties of
ionic liquids in order to improve the transesterication reaction
(Table 12). Their rst objective is to immobilize and recycle the
catalyst in the ionic phase.
When the reaction is catalysed by a base (MeONa) immobilized
in a phosphonium dicyanamide ionic liquid, a large excess of
methanol (molar ratio methanol:oil = 30:1) is necessary to yield a
high conversion. The reaction medium is monophasic at the end of
the reaction and methanol evaporation is necessary to separate the
methyl ester and ionic liquid phase. The latter can be recycled but a
rapid decay in catalytic activity is observed, probably due to
Reuse of enzyme
[508]
deactivation of methoxide by traces of free fatty acids or water

[509]. Similar deactivation was observed for a catalytic system
composed of Cs2CO3 in [BMI][NTf2]. Although it was possible to use
a lower excess of methanol with this latter system, the amount of
monoglyceride in biodiesel was above the limit imposed by
European or American specications [510].
Several Lewis acids were screened as catalyst in [BMI][PF6]
[511] or [BMI][InCl4] ionic liquids [512]. For most of the Lewis acids
biodiesel yield were very low. The best results were obtained with
Sn(3-hydroxy-2-methyl-4-pyrone)2(H2O)2
but unfortunately
recycling of the catalyst was prevented by its decomposition
under the reaction conditions.
The use of sulphuric acid in [BMI][NTf2] allows the formation of
biodiesel in high yield. The acid is almost completely retained in
the ionic liquid phase and the recovered IL can be reused at least six
times without any signicant loss in biodiesel yield or selectivity.
However, a large excess of methanol and long reaction times are
required, and the amount of residual glycerides in biodiesel is
above specications.
The transesterication reaction can also be catalysed by
Brnsted or Lewis acid ionic liquids. SO3-H functional Brnsted
acidic ionic liquids were described for the transesterication of
cottonseed oil or waste oil at 170 8C [513,514]. 1-(4-Sulfonic acid)
butylpyridinium hydrogen sulfate showed the best catalytic
performance, which is nearly the same as that of concentrated
sulphuric acid. With chloroaluminate ionic liquids [Et3NH][ClAlCl3] (x(AlCl3) = 0,7) it was possible to perform the reaction at a
lower temperature (70 8C) with good yield. The catalyst was
recycled for six times and the yield remained unchanged. However
the catalyst could be destroyed by the presence of water in the
reactant [515].
Ionic liquids can also be used as a medium for lipase catalysed
production of biodiesel [508,516]. The biodiesel is separated by
simple decantation and the recovered ionic liquid/enzyme system
can be reused at least four times without loss of catalytic activity
and selectivity.
Ionic liquids have also been considered for the purication of
biodiesel. An equimolar mixture of triethylammonium chloride
with glycerol has been used to extract excess glycerol from
biodiesel formed from the reaction of soy bean oil with ethanol.
The analysis of the biodiesel layer showed complete removal of
glycerol while the lower layer was enriched in glycerol. However,
no simple method for recovering the glycerol and the quaternary
ammonium salt from the washing eutectic is available at present
[517].
51
Scheme 61. Ethenolysis of methyloleate.
7.3.2. Methyloleate metathesis

Methyl esters arising from the transesterication of vegetable
oils can be converted into high value compound by a metathesis
reaction. Ethenolysis of methyl oleate is expected to produce 1decene and methyl-9-decenoate, two useful intermediates for the
production of lubricants and polyesters (Scheme 61) [518].
The metathesis reaction catalysed by different Ru catalysts has
been reported in [BMI] or [BMMI][NTf2] ILs [519]. High conversion
and selectivity were obtained with Hoveyda I catalyst but the
reaction required a high catalyst loading (5 mol%). Complexes
bearing ionic tags were found to be poorly recyclable under
ethenolysis reaction.
8. General conclusion and perspectives
The aim of this review was not to give an exhaustive, full
description of all the catalytic reactions that can be performed in
ILs. Our objective was rather to stand back from the huge quantity
of publications and patents and to try to give a general overview of
what can be done. In this context, many topics have not been
broached while being the object of much interest.
One can mention the increasing interest for the use of ILs in
biocatalysis reactions [34,35]. Surprisingly, enzymes of quite
diverse types could stay active in ILs in presence of more or less
water. ILs may offer advantages to this eld in terms of better
solubility of substrates compared to water, improved thermal and
operational stabilities, sometimes enhanced enzyme regio- or
enantio-selectivity, and the high potential of integration of the
separation in the reaction, facilitated by the low vapour pressure of
ILs. However, the properties of ILs that may affect the catalytic
behaviours of enzymes is not yet quite clear. Could the aqueous
solution of free enzyme be embedded in the IL nano-structure
network? What quantitative advantages can be expected from
using ILs in bio-transformations? The data, extracted from open
literature, reveal the high degree of variation in the published
results which only permits semi-quantitative comparisons [520].
Ionic liquids present the potential to have a huge impact on
organo-catalysis [521]. This potential has been demonstrated in
Diels-Alder reactions in which ILs can display interesting Hbonding with the reactants and then can direct the reaction
selectivity. Imidazolium-derived organocatalysts which can be
recycled because of their insolubility have also been reported.
Another interesting topic, not discussed in this review, is the
combination of ILs with an electrochemical process [29,522]. ILs
were indeed rst developed as low-temperature liquid electrolytes
because of their good electrical conductivity. But so far, their use
for electrocatalysis or electrosynthesis is not as developed as it
could have been expected. For example, ionic liquids can offer
advantages because they combine different properties such as
good conductors of electricity, avoiding the use of supporting salts,
and potential active species stabilisers such as Pd or Pt
nanoparticles or others. The in situ electrochemical generation
of H2O2 or the activation of oxygen for olen epoxidation are
examples of the potential of ILs. The combination of ILs with
sonochemistry can also be an interesting approach for process
intensication provided that ILs remain stable under exposure to
ultra-sounds. In another approach, carbon ionic liquid composite
electrodes (CILE) have recently been proposed and used as
convenient electrodes for different electrochemical applications
[523]. It is well-known that electrochemical activation and
conversion of CO2 can provide an interesting solution to overcome

its thermodynamic stability and kinetic inertness. In the case of
electro-reduction of CO2, the change of medium, whether or not it
is aprotic, or the electrode can change the nature of the products
generated. In this context, ILs can open windows because of the
possibility to tune their polarity, miscibility with water and protic
character [524]. In this area, electrocatalytic synthesis of organic
carbonates from carbon dioxide and alcohols or phenols have also
been reported using ILs [525,526].
Another breakthrough concerns the preparation of new
inorganic materials in purely ionic media. To give just one
example, novel zeotype frameworks (aluminophosphates) could
be synthesised with an IL serving as both solvent and template
agent [527]. ILs can offer very specic ways of interactions with
their different degrees of order from liquid crystals to extended
hydrogen-bonding network, polar and non polar regions. They may
be new all in one systems acting together as solvent-templatereactants [528]. The new materials generated, with sometimes
unprecedented and otherwise inaccessible structures, could open
the way to the discovering new catalytic supports. Finally the
introduction of cyclohexane on an imidazolium moiety can permit
access to derivatives with very low vapour pressure, high density
chemical and thermal stability. Hydrocarbons can be considered as
a liquid storage medium for H2 if they can be hydrogenated or
dehydrogenated. These imidazolium salts can add reversibly 612
hydrogens per ionic pair in the presence of classical hydrogenation/dehydrogenation nanoparticle catalysts based on Pd(0) or
Ir(0). Compressed hydrogen gas can only hold 15 g/L at 350 atm.
These ILs could hold up to 30 g/L of H2 at atmospheric pressure.
Despite the potential interest of this concept on paper, it is worth
mentioning that the dehydrogenation process remains the key
factor due to the endothermicity of alkane dehydrogenation. The
reaction occurs at T > 200 8C, under an inert atmosphere to avoid
ILs decomposition [529].
Acknowledgements
We thank J. Vedrine for his invitation to write this review. We
also thank C. Vallee for his kind contribution to this review and for
instructive discussions. The authors are thankful for the manuscripts anonymous reviewers contribution, for their constructive
comments and advices. The IFP is gratefully acknowledged for
providing us support and assistance.
We would like to dedicate this review to Y. Chauvin in honor of
his pioneering contribution in the eld of ionic liquids and his
continuous assistance.
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Ionic Liquids and Catalysis

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Applied Catalysis A: General 373 (2010) 156

Contents lists available at ScienceDirect

Applied Catalysis A: General

Ionic liquids and catalysis: Recent progress from knowledge to applications

H. Olivier-Bourbigou et al. / Applied Catalysis A: General 373 (2010) 156

Latest advances in the preparation and purication of ILs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

H. Olivier-Bourbigou et al. / Applied Catalysis A: General 373 (2010) 156

The performance of an IL will strongly depend on the technology in

Fig. 1. Evolution of IL generations.

H. Olivier-Bourbigou et al. / Applied Catalysis A: General 373 (2010) 156

and not their similarities. Some of the properties described some

described in open literature and can be easily found in a good

H. Olivier-Bourbigou et al. / Applied Catalysis A: General 373 (2010) 156

Scheme 1. Main cations and anions described in literature.

in practical catalytic applications. It plays a major role in stirring,

chemical properties. Protic ILs and Brnsted and/or Lewis ILs

2.2. A widening range of ionic liquids available

Fig. 2. Typical polarity and volatility characteristics of alternative solvents.

H. Olivier-Bourbigou et al. / Applied Catalysis A: General 373 (2010) 156

Scheme 2. ILs with targeted properties (decrease viscosity and density).

Scheme 3. New methimazole based ILs.

and for substituents at the cation (such as PEG-functionalised

is replaced with ILs based on dicyanamide anions, have been

H. Olivier-Bourbigou et al. / Applied Catalysis A: General 373 (2010) 156

Scheme 4. Examples of ILs with targeted functions.

Scheme 5. Cost-effective ILs.

Scheme 6. Bio ILs.

H. Olivier-Bourbigou et al. / Applied Catalysis A: General 373 (2010) 156

base). They present the advantage of being cost-effective and easily

Scheme 8. N,N-dimethylethanolammonium formate ILs.

low temperatures compared with their alkylated homologues

H. Olivier-Bourbigou et al. / Applied Catalysis A: General 373 (2010) 156

Scheme 9. Acid and basic ILs.

containing polynuclear metallic anions such as chloroaluminates,

Scheme 10. Examples of basic ILs.

Scheme 11. Example of switchable Lewis basic ILs.

H. Olivier-Bourbigou et al. / Applied Catalysis A: General 373 (2010) 156

ILs, can dramatically modify their acido-basic properties. The

2.2.4. Chiral ILs

Scheme 13. Examples of chiral ILs.

H. Olivier-Bourbigou et al. / Applied Catalysis A: General 373 (2010) 156

Scheme 17. Two-steps formation of Ag based hydrophobic ILs (L = olen or

Scheme 14. Chiral ephedrinium based ILs.

2.2.6. ILs at the frontier between organic and inorganic materials

Scheme 15. Example of silica supported CIL.

hydroxy functionality of the cation plays an important role in the

Scheme 16. Switchable Polarity Solvents (SPS).

2.2.6.2. Deep eutectic solvents (DES). Recently, some deep eutectic

H. Olivier-Bourbigou et al. / Applied Catalysis A: General 373 (2010) 156

2.3. Latest advances in the preparation and purication of ILs

Eutectic for 3:7 molar ratio

Eutectic for 2:1 molar ratio

Dependent upon the number of acid functionalities

Eutectic for 4.8:1 molar ratio

Eutectic for 4:1molar ratio

Eutectic for 3:1 molar ratio

limited by the availability of the acid (HX) or [NH4]+ salts. These

H. Olivier-Bourbigou et al. / Applied Catalysis A: General 373 (2010) 156

Scheme 19. Direct access to functionalised ILs.

an ionic liquid. However the stability of these ILs remains limited at

limits of detection (when available) have been compiled [150].

H. Olivier-Bourbigou et al. / Applied Catalysis A: General 373 (2010) 156

physico-chemical properties such as viscosity, density, surface