Catalysis in ionic liquids

The wide range of reactions that have been undertaken in low temperature ionic hquid solvents is quite remarkable. It is limited simply by ones imagination. The specific and tuneable solvent properties of ionic liquids are a key feature for their use as solvents and have 

1 Reactions involving first generation chloroaluminate(lll) ionic liquids 

The chloroaluminate ionic liquid mixtures are governed by the following primary equilib- 

This is an acid base equilibrium under the Franklin definition. The [AI2CI7] species is the acid and the Cl is the base. Note that this is an aprotic equihbrium. Therefore if the mole ratio of [Q-mimjCkAlCla is greater than, less than, or exactly equal to 50 50, flic solvent behavior can be described as Franklin basic, Franklin acidic, or neutral. 

Considering that aluminum trichloride is a very important commercial catalyst wifli over 25,000 tonnes produced annually in the USA alone, such hquids containing aluminum trichloride and allowing for differing levels of acidity have been extensively studied as first generation ionic catalytic solvents in a wide variety of synthetic and catalytic processes. Ionic liquids could therefore be used as substitutes for conventional solid or suspended sources of aluminum(III) chloride. As liquid phase catalysts, they allow for tremendous control of reactor inventories and can be cleaned and recycled with ease. Therefore, ionic liquids, in ideal cases, have no waste associated with them, whereas the supported alumi-num(III) chloride catalysts will require large (and annually rising) waste disposal costs. 

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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). 

Scheme 5.2-1 Early examples of transition metal catalysis in ionic liquids.

The author anticipates that the further development of transition metal catalysis in ionic liquids will, to a significant extent, be driven by the availability of new ionic liquids with different anion systems. In particular, cheap, halogen-free systems combining weak coordination to electrophilic metal centers and low viscosity with high stability to hydrolysis are highly desirable. 

Probably the most prominent property of an ionic liquid is its lack of vapor pressure. Transition metal catalysis in ionic liquids can particularly benefit from this on economic, environmental, and safety grounds. 

Obviously, with the development of the first catalytic reactions in ionic liquids, the general research focus turned away from basic studies of metal complexes dissolved in ionic liquids. Today there is a clear lack of fundamental understanding of many catalytic processes in ionic liquids on a molecular level. Much more fundamental work is undoubtedly needed and should be encouraged in order to speed up the future development of transition metal catalysis in ionic liquids. 

However, research into transition metal catalysis in ionic liquids should not focus only on the question of how to make some specific products more economical or ecological by use of a new solvent and, presumably, a new multiphasic process. Since it bridges the gap between homogeneous and heterogeneous catalysis, in a novel and highly attractive manner, the application of ionic liquids in transition metal catalysis gives access to some much more fundamental and conceptual questions for basic research. 

In comparison with traditional biphasic catalysis using water, fluorous phases, or polar organic solvents, transition metal catalysis in ionic liquids represents a new and advanced way to combine the specific advantages of homogeneous and heterogeneous catalysis. In many applications, the use of a defined transition metal complex immobilized on a ionic liquid support has already shown its unique potential. Many more successful examples - mainly in fine chemical synthesis - can be expected in the future as our loiowledge of ionic liquids and their interactions with transition metal complexes increases. 

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). 

INTRODUCTION TO TRANSITION METAL CATALYSIS IN IONIC LIQUIDS... 

In comparison to traditional biphasic catalysis using water, fluorous phases or polar organic solvents, transition metal catalysis in ionic liquids represents a new and advanced way of combining the specific advantages of homogeneous and heterogeneous catalysis. 

A summary of the research activities of the last four years reveals three different important trends (a) The design of new ionic ligands for excellent catalyst immobilisation in ionic liquids and high regioselectivity (b) the successful application of cheap, halogen-free ionic liquids in the biphasic Rh-catalysed hydroformylation (c) the successful development of unusual multiphasic reaction concepts for Rh-catalysed hydroformylation, namely catalysis in ionic liquid/supercritical C02 and SILP-catalysts. 

A major step towards applicability of multiphase catalysis in ionic liquids is the development of Supported Ionic Liquid Phase (SLIP) -catalysis by the Wasserscheid group [28,29]. The SLIP concept enables quasi-heterogeneous catalysis in ionic liquids and opens the door to the production of basic chemicals. 

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