Introducing Ionic Liquids

The last two decades have seen an explosion of interest in ionic liquids [1]. Their use as solvents has been the subject of widespread academic study [2] and they have been applied in a number of commercial processes [3]. Much of the interest in ionic liquids has centered on their possible use as green solvents [4]. However, this has been the subject of much controversy [5], and the concept of a green solvent itself is now somewhat dated. There have been many reviews of ionic liquids. Some of these have focused on particular applications, for example, analysis [6], biocatalysis [7], catalysis [8], electrochemical devices [9], or engineering fluids [10]. Others have concentrated on particular subgroups of ionic liquids, for example, task-specific ionic liquids [11]. This chapter summarizes what is known about the physicochemical properties that are of particular interest for supported ionic hquid phases (SILPs). 

Supported Ionic Liquids Fundamentals and Applications, First Edition. 

Edited by Rasmus Fehrmann, Anders Riisager, and Marco Haumann. 

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In summary, the formation of self-assemblies in ionic liquids is a general phenomenon that depends on the molecular structures of amphiphUes, ionic liquids, and their combinations. The ether-introduced ionic liquids facilitate the formation of molecular self-assemblies. However, stable self-assemblies can form also in conventional ionic liquids if the intermolecular interactions are suitably tuned. 

An ionic liquid supported Pd catalyst, [NB4MPy ][BF4 ]Pd (acac)/AC with a nominal Pd loading of 0.3 wt.% was prepared and characterized in this work. According to the XPS analysis Pd was not in reduced state after the reduction at 100°C - 120°C. The specific surface area, micropore volume and the pore diameter decreased after introducing ionic liquid into support, by 32%, 32% and, 18% respectively, compared to the active carbon support. SEM images from a ftesh and a spent [NB4MPy ][BF4 ]Pd(acac)/AC catalysts revealed that... 

In the 1990, Chauvin and coworkers have introduced ionic liquids (ILs) - especially those derived from the combination of quaternary ammonium salts and weakly coordinating anions - as immobilizing agents for various classical transition metal catalyst precursors in reactions [1]. In particular, these liquids provide more adequate and favorable environment for carbonylation reactions as compared to those performed in classical organic solvents or water. The vast majority of these compounds a) are effectively nonvolatile (most of them exhibit negligible vapor pressure) ... 

The pyridinium- and the imidazolium-based chloroaluminate ionic liquids share the disadvantage of being reactive with water. In 1990, Mike Zaworotko (Eigure 1.4) took a sabbatical leave at the Air Eorce Academy, where he introduced a new dimension to the growing field of ionic liquid solvents and electrolytes. 

Despite the utility of chloroaluminate systems as combinations of solvent and catalysts in electrophilic reactions, subsequent research on the development of newer ionic liquid compositions focused largely on the creation of liquid salts that were water-stable [4], To this end, new ionic liquids that incorporated tetrafiuoroborate, hexafiuorophosphate, and bis (trifiuoromethyl) sulfonamide anions were introduced. While these new anions generally imparted a high degree of water-stability to the ionic liquid, the functional capacity inherent in the IL due to the chloroaluminate anion was lost. Nevertheless, it is these water-stable ionic liquids that have become the de rigueur choices as solvents for contemporary studies of reactions and processes in these media [5],... 

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. 

A similar catalytic dimerization system has been investigated [40] in a continuous flow loop reactor in order to study the stability of the ionic liquid solution. The catalyst used is the organometallic nickel(II) complex (Hcod)Ni(hfacac) (Hcod = cyclooct-4-ene-l-yl and hfacac = l,l,l,5,5,5-hexafluoro-2,4-pentanedionato-0,0 ), and the ionic liquid is an acidic chloroaluminate based on the acidic mixture of 1-butyl-4-methylpyridinium chloride and aluminium chloride. No alkylaluminium is added, but an organic Lewis base is added to buffer the acidity of the medium. The ionic catalyst solution is introduced into the reactor loop at the beginning of the reaction and the loop is filled with the reactants (total volume 160 mL). The feed enters continuously into the loop and the products are continuously separated in a settler. The overall activity is 18,000 (TON). The selectivity to dimers is in the 98 % range and the selectivity to linear octenes is 52 %. 

Section 6.2.1 offers literature data on the electrodeposition of metals and semiconductors from ionic liquids and briefly introduces basic considerations for electrochemical experiments. Section 6.2.2 describes new results from investigations of process at the electrode/ionic liquids interface. This part includes a short introduction to in situ Scanning Tunneling Microscopy. 

In addition to the examples described above, functionalized ionic liquids have been recently introduced as microwave-compatible soluble supports [137,138]. 

A basic ionic liquid, l-methyl-3-butylimidazolium hydroxide ([bmIm]OH) and l-butyl-3-methyl-methylimidazolium tetrafluoroborate ([bmim]BF4), has been introduced as a catalyst and reaction medium for the Markovnikov addition of imidazoles 116 to vinyl esters 115 under mild conditions to give imidazoesters 117 <06JOC3991 06TL1555>. A series of (nitroimidazolyl)succinic esters and diacids were prepared from the Michael-type addition of the nitroimidazole to the a,P-unsaturated ester <06S3859>. 

Many ionic liquids are based on N,N-dialkylimidazolium cations (BMI) which form salts that exist as liquids at, or below, room temperature. Their properties are also influenced by the nature of the anion e. g. BF T PFg. The C-2(H) in imidazole is fairly labile but the C-4(H) and the C-5(H) are less so. Under microwave-enhanced conditions it is therefore possible to introduce three deuterium atoms (Scheme 13.4). As hydrogen isotope exchange is a reversible reaction this means that the three deuterium atoms can be readily exchanged under microwave irradiation. For storage purpose it might be best to back-exchange the C-2(D) so that the 4,5-[2H2] isotopomer can be safely stored as the solid without any dangers of deuterium loss. The recently... 

These alternative processes can be divided into two main categories, those that involve insoluble (Chapter 3) or soluble (Chapter 4) supports coupled with continuous flow operation or filtration on the macro - nano scale, and those in which the catalyst is immobilised in a separate phase from the product. These chapters are introduced by a discussion of aqueous biphasic systems (Chapter 5), which have already been commercialised. Other chapters then discuss newer approaches involving fluorous solvents (Chapter 6), ionic liquids (Chapter 7) and supercritical fluids (Chapter 8). 

In contrast, we intend to demonstrate the principle aspects of catalyst recycling and regeneration using the ionic liquid methodology. These aspects will be explored in more detail for the example of Rh-catalysed hydroformylation (see Section 7.2). First, however, we will briefly introduce important general facts concerning transition metal catalysis in ionic liquids (see Section 7.1.2). This will be followed by a consideration of liquid-liquid biphasic reactions in these media from an engineering point of view (see Section 7.1.3). 

The term Supported Ionic Liquid Phase (SILP) catalysis has recently been introduced into the literature to describe the heterogenisation of a homogeneous catalyst system by confining an ionic liquid solution of catalytically active complexes on a solid support [68], In comparison to the conventional liquid-liquid biphasic catalysis in organic-ionic liquid mixtures, the concept of SILP-catalysis offers very efficient use of the ionic liquid. Figure 7.10 exemplifies the concept for the Rh-catalysed hydroformylation. 

In 2002 Mehnert and co-workers were the first to apply SILP-catalysis to Rh-catalysed hydroformylation [74], They described in detail the preparation of a surface modified silica gel with a covalently anchored ionic liquid fragment (Scheme 7.7). The complex N-3-(3-triethoxysilylpropyl)-4,5-dihydroimidazole was reacted with 1-chlorobutane to give the complex l-butyl-3-(3-triethoxysilylpropyl)- 4,5-dihydroimidazolium chloride. The latter was further treated with either sodium tetrafluoroborate or sodium hexafluorophosphate in acetonitrile to introduce the desired anion. In the immobilisation step, pre-treated silica gel was refluxed with a chloroform solution of the functionalised ionic liquid to undergo a condensation reaction giving the modified support material. Treatment of the obtained monolayer of ionic liquid with additional ionic liquid resulted in a multiple layer of free ionic liquid on the support. 

To introduce the Rh-centre in the supported ionic liquid, a solution of [Rh(CO)2(acac)] in acetonitrile was treated with either the ligand tri(m-sulfonyl)triphenyl phosphine trisodium salt (TPPTS) or the ligand tri(m-sulfonyl)triphenyl phosphine tris(l- butyl-3-methyl-imidazolium) salt (TPPTI) (Rh/P ratio of 1 10). The ligand TPPTI was found to dissolve in [BMIM][BF4] and... 

The primary source of error is ground loop currents. This is caused by galvanic errors introduced by small potentials resulting from the ionic liquids and dissimilar metals that the electrode is in contact with in a bioreactor. Additional sources of error are interactions with other electrodes. We have frequently found that a pH electrode not connected to an isolation amplifier that floats the reference can show errors of 1-2 pH units. A simple test is to measure the pH of a buffered solution on-line and off-line to check the accuracy of a measurement. 

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