Molten salts as reaction media

W. Sundermeyer Preparation of organosilicon halides in molten salts as reaction media, pp. 93-99 (16). 

The use of ionic liquids (also called molten salts) as reaction media is a relatively new area, although molten conditions have been well established in industrial processes (e.g. the Downs process, Fig. 11.2) for many years. While some molten salts are hot as the term suggests, others operate at ambient temperatures and the term ionic liquids is more appropriate. Although the terms ionic liquids and molten salts are sometimes used interchangeably, we make a clear distinction between them, using ionic liquid only for a salt with a melting point <373 K. 

The main advantages for using molten salts as reaction media may be summarized as follows ... 

Excision reactions are sometimes accompanied by redox chemistry. For example, dissolution of the 2D solid Na4Zr6BeCli6 in acetonitrile in the presence of an alkylammonium chloride salt results in simultaneous reduction of the cluster cores (144). Here, the oxidation product remains unidentified, but is presumably the solvent itself. As a means of preventing such redox activity, Hughbanks (6) developed the use of some room temperature molten salts as excision media, specifically with application to centered zirconium-halide cluster phases. A number of these solids have been shown to dissolve in l-ethyl-2-methylimidazolium chloride-aluminum chloride ionic liquids, providing an efficient route to molecular clusters with a full compliments of terminal chloride ligands. Such molten salts are also well suited for electrochemical studies. 

The use of ionic liquids as reaction media for the palladium-catalyzed Heck reaction was first described by Kaufmann et ak, in 1996 [85]. Treatment of bromoben-zene with butyl acrylate to provide butyl trans-cinnamate succeeded in high yield in molten tetraallcylammonium and tetraallcylphosphonium bromide salts, without addition of phosphine ligands (Scheme 5.2-16). 

This means that addition of elemental E to alkali metal polychalcogenide fluxes (200-600°C) will promote the formation of longer chains as potential ligands, when such molten salts are employed as reaction media for the preparation of polychalcogenide complexes. Speciation analysis for polychalcogenides in solution has been performed by a variety of physical methods including UV/vis absorption spectroscopy, Raman spectroscopy, Se, Te and Te NMR, electron spin resonance and electrospray mass spectrometry. 

Organic molten salts such as tris-n-butyl-dodecylphosphonium halides (melting point below 40°C) have been used as reaction media for nucleophilic aromatic substitution of aryl tosylates by halide ions (Fry and Pienta, 1985). 

The high melting points of molten salts prevent their use as reaction media for many practical and fundamental applications. For example, many organic substances have low boiling points and a low thermal stability and cannot be dissolved in molten salts. 

The first example of a Heck reaction in a molten salt stems from as early as 1996 when tetraalkylammonium and phosphonium halides were used as reaction media for the coupling between arylhalides and n-butyl acrylate. Particularly good results were achieved in trihexyl(tetradecyl)phosphonium chloride, both in terms of reactivity and ease of product isolation. 

Ionic liquids (room-temperature molten salts) with chiral cations were efficiently used as reaction media to prepare homochiral MOFs [33], But the use of homochiral ligands as precursors in the synthesis is even more efficient For instance, Lin et al. [34] prepared MOFs with BINOL (l,l -bi-2,2 -naphthol) and BINAP (2,2 -his(diphenylphosphino)-1,1 -binaphthyl) as chiral linkers. Unfortunately, attempts to use such chiral catalysts in asymmetric catalysis showed some but not high enantiomeric excess in the studied reactions, perhaps the flexibility of the ligands in the MOF framework is not sufficient to induce the chirality effect in the reactions. The most illustrative example was presented hy Lin [35] the reaction of asymmetric hydrogenation of aromatic ketones demonstrated a 99.2% ee for Ru-BINAP/MOF systems. 

In some cases, the Q ions have such a low solubility in water that virtually all remain in the organic phase. ° In such cases, the exchange of ions (equilibrium 3) takes place across the interface. Still another mechanism the interfacial mechanism) can operate where OH extracts a proton from an organic substrate. In this mechanism, the OH ions remain in the aqueous phase and the substrate in the organic phase the deprotonation takes place at the interface. Thermal stability of the quaternary ammonium salt is a problem, limiting the use of some catalysts. The trialkylacyl ammonium halide 95 is thermally stable, however, even at high reaction temperatures." The use of molten quaternary ammonium salts as ionic reaction media for substitution reactions has also been reported. " " ... 

Salt-inclusion solids described herein were synthesized at high temperature (>500°C) in the presence of reactive alkali and alkaline-earth metal halide salt media. For single crystal growth, an extra amount of molten salt is used, typically 3 5 times by weight of oxides. The reaction mixtures were placed in a carbon-coated silica ampoule, which was then sealed under vacuum. The reaction temperature was typically set at 100-150 °C above the melting point of employed salt. As shown in the schematic drawing in Fig. 16.2, the corresponding metal oxides were first dissolved conceivably via decomposition because of cor-... 

Much recent work on NaCl/AlCl3 and related haloaluminate systems has concerned their behaviour as molten salts and non-aqueous electrolytes, and their use as aprotic reaction media.345-352 A1C13 with n-butylpyridinium chloride, and allied low-melting combinations provide useful model systems for fused salt behaviour and have attracted considerable attention on this account.353-356 There is evidence, particularly from 27Al NMR spectra, that Al2Cly and also Al3Clr0 are present in AlCl3-rich systems.354,355... 

Salt and metal insoluble impurities, such as Pu02, associated with plutonium metal are taken up by the salt in Stage 1. Stage 2 is essentially free of these impurities. Strickland, et al. (14), reported that plutonium oxide extracts americium from molten plutonium metal in a molten salt media. Because these salt and metal insoluble impurities are present in sizable amounts only in Stage 1, the side reaction between americium and these impurities occurs only in Stage 1. The side reaction term (B) is introduced to quantify the side reaction caused by the presence of impurities such as in Stage 1. 

Molten salts at room temperature, so-called ionic liquids [1, 2], attracting the attention of many researchers because of their excellent properties, such as high ion content, liquid-state over a wide temperature range, low viscosity, nonvolatility, nonflammability, and high ionic conductivity. The current literature on these unique salts can be divided into two areas of research neoteric solvents as environmentally benign reaction media [3-7], and electrolyte solutions for electrochemical applications, for example, in the lithium-ion battery [8-12], fuel cell [13-15], solar cell [16-18], and capacitor [19-21],... 

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