Ionic liquids catalytic properties

Moreover, these experiments reveal some unique properties of the chlorostan-nate ionic liquids. In contrast to other known ionic liquids, the chlorostannate system combine a certain Lewis acidity with high compatibility to functional groups. The first resulted, in the hydroformylation of 1-octene, in the activation of (PPli3)2PtCl2 by a Lewis acid-base reaction with the acidic ionic liquid medium. The high compatibility to functional groups was demonstrated by the catalytic reaction in the presence of CO and hydroformylation products. 

The combination of ionic liquids with supercritical carbon dioxide is an attractive approach, as these solvents present complementary properties (volatility, polarity scale.). Compressed CO2 dissolves quite well in ionic liquid, but ionic liquids do not dissolve in CO2. It decreases the viscosity of ionic liquids, thus facilitating mass transfer during catalysis. The separation of the products in solvent-free form can be effective and the CO2 can be recycled by recompressing it back into the reactor. Continuous flow catalytic systems based on the combination of these two solvents have been reported [19]. This concept is developed in more detail in Section 5.4. 

The types of ionic liquids shown in Figure 5.4 have been most extensively studied, especially ones based on chloroaluminate. Whilst these chloroaluminate materials also display useful Lewis acid properties they are highly air and moisture sensitive, which renders them relatively commercially unattractive. Newer ionic liquids containing C104 and NOa anions, for example, which are less air and moisture sensitive, are now being more widely studied, but these are less catalytically active. Other than lack of vapour pressure and catalytic properties there are several other features common to most ionic liquids that make them attractive reaction solvents. These include ... 

The acidic and catalytic properties of chloroaluminate(iii) ionic liquids are frequently said to arise from the species AI2CI7" which is generated according to Equation (5.1). 

Nowadays, a number of commercial suppliers [20] offer ionic liquids, some of them in larger quantities, [21] and the quality of commercial ionic liquid samples has clearly improved in recent years. The fact that small amounts of impurities significantly influence the properties of the ionic liquid and especially its usefulness for catalytic reactions [22] makes the quality of an ionic liquid an important consideration [23]. Without any doubt the improved commercial availability of ionic liquids is a key factor for the strongly increasing interest in this new class of liquid materials. 

An ionic liquid can be used as a pure solvent or as a co-solvent. An enzyme-ionic liquid system can be operated in a single phase or in multiple phases. Although most research has focused on enzymatic catalysis in ionic liquids, application to whole cell systems has also been reported (272). Besides searches for an alternative non-volatile and polar media with reduced water and orgamc solvents for biocatalysis, significant attention has been paid to the dispersion of enzymes and microorganisms in ionic liquids so that repeated use of the expensive biocatalysts can be realized. Another incentive for biocatalysis in ionic liquid media is to take advantage of the tunability of the solvent properties of the ionic liquids to achieve improved catalytic performance. Because biocatalysts are applied predominantly at lower temperatures (occasionally exceeding 100°C), thermal stability limitations of ionic liquids are typically not a concern. Instead, the solvent properties are most critical to the performance of biocatalysts. 

In addition to their use as solvents, surfactants, and biocides, ionic liquids are attractive for use in catalytic reactions due to their ability to activate reactant molecules, the ease of separation from final products, thermal stability, solubility of gaseous reactants, among other properties. Amit Gujar and Mark White (Mississippi State Univ., USA) show, for example,... 

Ionic liquids have very low volatilities and are easily recycled. Many of these materials can act as both a solvent and a catalyst depending on their Lewis acidities and other properties. These catalytically active solvents can eliminate the need to use additional catalysts that may be toxic or may produce large amounts of wastes. Reactions in ionic liquids are usually carried out under mild conditions, and the products are often easily removed from the solvent by phase separation or low-pressure distillation from the ionic liquid. 

Ionic liquids are attracting increasing interest as environmentally benign solvents, because they possess a number of interesting properties. Among these, one of the most important is their virtually non-existent vapor pressure, which makes them easily confinable and also allows easy recyclability of catalytic systems after distillation of volatile products. 

A review of solvent properties of, and organic reactivity in, ionic liquids demonstrates the relatively small number of quantitative studies of electrophilic aromatic substitution in these media.3 Studies mentioned in the review indicate conventional polar mechanisms. 1-Methylpyrrole reacts with acyl chlorides in the ionic liquid 1-butylpyridinium tetrafluoroborate to form the corresponding 2-acylpyrrole in the presence of a catalytic amount of ytterbium(III) trifluoromethanesulfonate.4 The ionic liquid-catalyst system is recyclable. Chloroindate(III) ionic liquids5 are catalytic media for the acylation, using acid chlorides and anhydrides, of naphthalene, benzene, and various substituted benzenes at 80-120 °C. Again the ionic liquid is recyclable. 

For catalytic application where a transition metal catalyst is dissolved in the ionic liquid or the ionic liquid itself acts as the catalyst two additional aspects are of interest. Firstly, the special solubility properties of the ionic liquid enables a biphasic reaction mode in many cases. Exploitation of the miscibility gap between the ionic catalyst phase and the products allows, in this case, the catalyst to be isolated effectively from the product and reused many times. Secondly, the non-volatile nature of ionic liquids enables a more effective product isolation by distillation. Again, the possibility arises to reuse the isolated ionic catalyst phase. In both cases, the total reactivity of the applied catalysts is increased and catalyst consumption relative to the generated product is reduced. For example, all these advantages have been convincingly demonstrated for the transition metal catalysed hydroformylation [17]. 

This simple example may illustrate that in general the reaction of an organic halide salt [cation]X with an excess of a Lewis-acid MXy can result in new catalytic materials even if other Lewis-acids are applied than AICI3. In contrast, the use of other Lewis-acids to form the ionic liquid of type [cation][MXy+i] + excess MXy (the excess of MXy may be dissolved in the neutral ionic liquid or may form acidic anionic species such as e.g. [M2X2y+i]-) gives access to new combinations of properties (e.g. a liquid, less oxophilic, Lewis-acidic catalyst with defined solubility and acidity properties). In Table 2 other examples of ionic liquids are presented which are formed by the reaction of an organic halide salt with different Lewis-acids. All these systems should be in principle useful acidic catalysts for synthetic organic chemistry even if not all displayed examples have been already discribed in the literature for this application. 

The synthesis of several hydrogensulphate and tetrakis(hydrogensulphato)borate ionic liquids has been described by our group [29]. Mixtures of these ionic liquids with sulphuric acid were used as non-volatile acidic phases with tuneable solubility properties for catalytic applications such as e.g. the alkylation of benzene with 1-decene. 

Nevertheless, the use of ILs in their liquid form presents some inconveniences in an industrial continuous system. Immobilising these ILs on inert supports on the other hand brings many advantages for the system, e.g. the easier separation of the catalyst from the reaction media and the possible utilisation of the catalyst in a continuous system. The evaluation of the catalytic properties of acidic ionic liquids, immobilised on known supports, and research of the possible advantages of these materials was the driving force of this work. 

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