Ionic liquids reviews

Ionic liquids have become a focus of increasing interest over the last decade.1 Some of this interest is due to their possible use as greener alternatives to volatile organic solvents (see below). There is, however, also a great deal of fundamental interest in how the unusual solvent environment that they present might affect reactions conducted in them. Recently, there have been a number of excellent ionic liquid reviews concerning their chemical and physical properties,2 and applications in synthesis and catalysis.1,3,4 It is remarkable that in 1999 it was possible to... 

E. (2010) Thermophysical properties of pure ionic liquids review of present situation. Ind. Eng. Chem. Res., 49,... 

Giroud, N.M., Rouault, H., Chainet, E., Poignet, J.C. (2008). Ionic liquids based electrolytes for lithium ion battery. ECS Meeting Abstracts, 802., 3044., 1091-8213 Gollei, A., Vass, A., PaUai, E., Gerzson, M, Ludanyi, L., Mink, J. (2009). Apparatus and method to measme dielectric prop>erties (e and e") of ionic liquids. Review of Scientific Instruments, 80., 4., 0034-6748... 

Maginn, E.J. (2009). Atomistic simulation of ionic liquids Reviews in Computational Chemistry vol 26 Ed. K B Lipkowitz, R Larter and T Cundari 2009 (Hoboken, NJ Wiley). 

For a review of salts formerly thought of as low-temperature ionic liquids, see Mamantov, G., Molten salt electrolytes in secondary batteries, in Materials for Advanced Batteries (Murphy, D. W., Broadhead, J., and Steele, B.C. H. eds.). Plenum Press, New York, 1980,... 

Thus, most ionic liquids are formed from cations that do not contain acidic protons. A summary of the applications and properties of ionic liquids may be found in a number of recent review articles [3]. The most common classes of cations are illustrated in Figure 2.1-1, although low melting point salts based on other cations, such as complex poly cationic amines [4] and heterocycle-containing drugs [5], have also been prepared. 

An alternative avenue for the exploration of the polarity of a solvent is by investigation of its effect on a chemical reaction. Since the purpose of this book is to review the potential application of ionic liquids in synthesis, this could be the most productive way of discussing ionic liquid polarity. Again, the field is in its infancy, but some interesting results are beginning to appear. 

The early history of ionic liquid research was dominated by their application as electrochemical solvents. One of the first recognized uses of ionic liquids was as a solvent system for the room-temperature electrodeposition of aluminium [1]. In addition, much of the initial development of ionic liquids was focused on their use as electrolytes for battery and capacitor applications. Electrochemical studies in the ionic liquids have until recently been dominated by work in the room-temperature haloaluminate molten salts. This work has been extensively reviewed [2-9]. Development of non-haloaluminate ionic liquids over the past ten years has resulted in an explosion of research in these systems. However, recent reviews have provided only a cursory look at the application of these new ionic liquids as electrochemical solvents [10, 11]. 

The measurement of correlation times in molten salts and ionic liquids has recently been reviewed [11] (for more recent references refer to Carper et al. [12]). We have measured the spin-lattice relaxation rates l/Tj and nuclear Overhauser factors p in temperature ranges in and outside the extreme narrowing region for the neat ionic liquid [BMIM][PFg], in order to observe the temperature dependence of the spectral density. Subsequently, the models for the description of the reorientation-al dynamics introduced in the theoretical section (Section 4.5.3) were fitted to the experimental relaxation data. The nuclei of the aliphatic chains can be assumed to relax only through the dipolar mechanism. This is in contrast to the aromatic nuclei, which can also relax to some extent through the chemical-shift anisotropy mechanism. The latter mechanism has to be taken into account to fit the models to the experimental relaxation data (cf [1] or [3] for more details). Preliminary results are shown in Figures 4.5-1 and 4.5-2, together with the curves for the fitted functions. 

The field of reaction chemistry in ionic liquids was initially confined to the use of chloroaluminate(III) ionic liquids. With the development of neutral ionic liquids in the mid-1990s, the range of reactions that can be performed has expanded rapidly. In this chapter, reactions in both chloroaluminate(III) ionic liquids and in similar Lewis acidic media are described. In addition, stoichiometric reactions, mostly in neutral ionic liquids, are discussed. Review articles by several authors are available, including Welton [1] (reaction chemistry in ionic liquids), Holbrey [2] (properties and phase behavior), Earle [3] (reaction chemistry in ionic liquids), Pagni [4] (reaction chemistry in molten salts), Rooney [5] (physical properties of ionic liquids), Seddon [6, 7] (chloroaluminate(III) ionic liquids and industrial applications), Wasserscheid [8] (catalysis in ionic liquids), Dupont [9] (catalysis in ionic liquids) and Sheldon [10] (catalysis in ionic liquids). 

Examples of reactions that have been carried out in these antimony(III) ionic liquids include the cyclizations of l,2-bis-(9-anthryl)-ethane (Scheme 5.1-12) and 1,2-bis-(l-naphthyl)-ethane (Scheme 5.1-13). A more detailed review of antimony(III) chloride molten salt chemistry has been published by Pagni [4]. 

Very recently, Olivier-Bourbigou and Magna [15], Sheldon [16], and Gordon [17] have published three excellent reviews presenting a comprehensive overview of current work in transition metal catalysis involving ionic liquids, with slightly different emphases. All three update previously published reviews on the same topic, by Wasserscheid and Keim [18], Welton [19] and Seddon and Holbrey [20]. 

For the results reported in both Table 7.2-3 and Table 7.2-4, the only reported detail concerning the ionic liquid was that it was [EMIM][C1-A1C13]. No details of the aluminium(III) chloride content were forthcoming. As with most of the work presented in this chapter, data are taken from the patent literature and not from peer reviewed journals, and so many experimental details are not available. This lack of clear reporting complicates issues for the synthetic polymer chemist. Simpler and cheaper chloroaluminate(III) ionic liquids prepared by using cations derived from the reaction between a simple amine and hydrochloric acid (e.g., Me3N-E3Cl and... 

Room temperature ionic liquids arc currently receiving considerable attention as environmentally friendly alternatives to conventional organic solvents in a variety of contexts.144 The ionic liquids have this reputation because of their high stability, inertness and, most importantly, extremely low vapor pressures. Because they are ionic and non-conducting they also possess other unique properties that can influence the yield and outcome of organic transformations. Polymerization in ionic liquids has been reviewed by Kubisa.145 Commonly used ionic liquids are tetra-alkylammonium, tetra-alkylphosphonium, 3-alkyl-l-methylimidazolium (16) or alkyl pyridinium salts (17). Counter-ions are typically PF6 and BF4 though many others are known. 

Abstract Current microwave-assisted protocols for reaction on solid-phase and soluble supports are critically reviewed. The compatibility of commercially available polymer supports with the relatively harsh conditions of microwave heating and the possibilities for reaction monitoring are discussed. Instrmnentation available for microwave-assisted solid-phase chemistry is presented. This review also summarizes the recent applications of controlled microwave heating to sohd-phase and SPOT-chemistry, as well as to synthesis on soluble polymers, fluorous phases and functional ionic liquid supports. The presented examples indicate that the combination of microwave dielectric heating with solid- or soluble-polymer supported chemistry techniques provides significant enhancements both at the level of reaction rate and ease of purification compared to conventional procedures. 

In recent years ionic liquids have also been employed as media for reactions catalyzed both by isolated enzymes and by whole cells, and excellent reviews on this topic are already available [47]. Biocatalysis has been mainly conducted in those room-temperature ionic liquids that are composed of a 1,3-dialkylimidazolium or N-alkylpyridinium cation and a noncoordinating anion [47aj. 

Welton, T., Room-Temperature Ionic Liquids. Solvents for Synthesis and Catalysis, Chemical Review, Vol. 99, No. (8), 1999,pp.2071-2083. 

The most important biphasic liquid systems are probably those that combine a conventional organic phase with another type of solvent, such as water, a fluorous organic solvent, or an ionic liquid [3]. In those cases the solvent can be considered as the support for the catalyst phase and we have therefore limited the examples in this review to those where the recycled liquid catalyst phase is recovered as a whole. 

From reviewing much of the literature it is easy to conclude that ionic liquids are excellent solvents for catalysts and reagents but not for products, which is obviously not the case. Whilst some products can be decanted from the liquid and others can be recovered by distillation, there are many useful reactions in which removal of the product (or residual reactants) from the ionic liquid is challenging. Extraction with an organic solvent, or even water, would reduce the overall eco-efficiency. Initial... 

The use of ionic liquids (ILs) to replace organic or aqueous solvents in biocatalysis processes has recently gained much attention and great progress has been accomplished in this area lipase-catalyzed reactions in an IL solvent system have now been established and several examples of biotransformation in this novel reaction medium have also been reported. Recent developments in the application of ILs as solvents in enzymatic reactions are reviewed. 

Binnemans, K. (2005) Ionic Liquid Crystals. Chemical Reviews, 105, 4148-4204. 

Dupont, J., de Souza, R.F. and Suarez, P.A.Z. (2002) Ionic liquid (molten salt) phase organometallic catalysis. Chemical Reviews, 102 (10), 3667-3691. 

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