Haloaluminate anion

The synthesis ofhaloaluminate-based ionic liquids from halide salts and aluminum Lewis acids (most commonly AIX3 X=C1, Br) can generally be split into two steps (i) fomation of the desired cation by the reaction of a trialkylamine, trialkylphosphine or dialkylsulfide with a haloalkane, and (ii) formation of the haloaluminate anion by addition of an appropriate aluminum halide to this salt (Scheme 2.1). 

For forty years following the introduction of haloaluminate-based ionic liquids by Hurley and Wier, [44, 45] the majority of research in this field was carried out on systems which were reactive with air and, more specifically, with water. The difficulty of working with these materials, using elaborate Schlenk-line airless techniques or expensive and difficult-to-maintain controlled-atmosphere glove boxes, had the effect of limiting the research to four American-based research groups, mostly funded by the US Air Force [46]. Well aware of this limitation, John Wilkes and coworkers made the decision to substitute the reactive haloaluminate anion... 

Room-temperature ionic liquids have recently attracted a great deal of industrial interest (Carmichael, 2000 Guterman, 1999 see also the brief overview by Earle et al. (2003) and the extensive and detailed review by Olivier-Bourbigou et al. (2010). They are versatile as solvents or nonsolvents for organic substances, and some exhibit strongly temperature-dependent water solubility. They are nonvolatile. Some, notably those containing haloaluminate anions, have widely variable Lewis and Brpnsted acidity (into the superacid range). Others, such as those with tetrafluoroborate or hexafluorophosphate... 

The viscosities of non-haloaluminate ionic liquids are also affected by the identity of the organic cation. For ionic liquids with the same anion, the trend is that larger allcyl substituents on the imidazolium cation give rise to more viscous fluids. For instance, the non-haloaluminate ionic liquids composed of substituted imidazolium cations and the bis-trifyl imide anion exhibit increasing viscosity from [EMIM], [EEIM], [EMM(5)IM], [BEIM], [BMIM], [PMMIM], to [EMMIM] (Table 3.2-1). Were the size of the cations the sole criteria, the [BEIM] and [BMIM] cations from this series would appear to be transposed and the [EMMIM] would be expected much earlier in the series. Given the limited data set, potential problems with impurities, and experimental differences between laboratories, we are unable to propose an explanation for the observed disparities. 

The addition of co-solvents to ionic liquids can result in dramatic reductions in the viscosity without alteration of the cations or anions in the system. The haloaluminate ionic liquids present a challenge, due to the reactivity of the ionic liquid. Nonetheless, several compatible co-solvents including benzene, dichloromethane, and acetonitrile have been investigated [33-37]. The addition of as little as 5 wt. % acetonitrile or 15 wt. % benzene or methylene chloride was able to reduce the... 

It must be noted that impurities in the ionic liquids can have a profound impact on the potential limits and the corresponding electrochemical window. During the synthesis of many of the non-haloaluminate ionic liquids, residual halide and water may remain in the final product [13]. Halide ions (Cl , Br , I ) are more easily oxidized than the fluorine-containing anions used in most non-haloaluminate ionic liquids. Consequently, the observed anodic potential limit can be appreciably reduced if significant concentrations of halide ions are present. Contamination of an ionic liquid with significant amounts of water can affect both the anodic and the cathodic potential limits, as water can be both reduced and oxidized in the potential limits of many ionic liquids. Recent work by Schroder et al. demonstrated considerable reduction in both the anodic and cathodic limits of several ionic liquids upon the addition of 3 % water (by weight) [14]. For example, the electrochemical window of dry [BMIM][BF4] was found to be 4.10 V, while that for the ionic liquid with 3 % water by weight was reduced to 1.95 V. In addition to its electrochemistry, water can react with the ionic liquid components (especially anions) to produce products... 

It is unclear at this time whether this difference is due to the different anions present in the non-haloaluminate ionic liquids or due to differences in the two types of transport number measurements. The apparent greater importance of the cation to the movement of charge demonstrated by the transport numbers (Table 3.6-7) is consistent with the observations made from the diffusion and conductivity data above. Indeed, these data taken in total may indicate that the cation tends to be the majority charge carrier for all ionic liquids, especially the allcylimidazoliums. However, a greater quantity of transport number measurements, performed on a wider variety of ionic liquids, will be needed to ascertain whether this is indeed the case. 

In general the potential windows are not as wide as those for the haloaluminates or the discrete anions and they tend to be limited by the deposition of metal at the cathodic limit and the evolution of chlorine at the anodic limit. Since ionic liquids are aprotic solvents, hydrogen evolution and hydrogen embrittlement that often occur in aqueous baths are circumvented in these liquids. Moreover, because of their thermal stability, these ionic liquids make it easier to electrodeposit crystalline metals and semiconductors through direct electrodeposition without subsequent annealing. 

So far, mostly solutions of heavy elements dissolved in ILs have been discussed. The p-block elements are peculiar in the sense that the haloaluminate ILs constitute an important class of ILs. However, unlike the more conventional cases, where the IL is composed of an organic cation and an organic anion or at most a simple inorganic ion like chloride, the haloaluminates are more complex. In aluminate ILs, the Al ion is an integral part of the IL and not, as discussed so far, a simple solute in an independent IL. As a result, both solutions of p-elements in regular ILs and systems like the haloaluminates will have to be discussed here. 

Within a series of non-haloaluminate ionic liquids containing the same cation, a change in the anion clearly affects the viscosity (Tables 3.2-1 and 3.2-3). The general order of increasing viscosity with respect to the anion is [(CF3S02)2N] <... 

The addition of cosolvents to ionic liquids can result in dramatic reductions in the viscosity without changing the cations or anions in the system. The haloalu-minate ionic liquids present a challenge due to the reactivity of the ionic liquid. Nonetheless, several compatible co-solvents have been investigated, including benzene, dichloromethane, and acetonitrile [13-17]. The addition of as little as 5 wt.% acetonitrile or 15 wt.% of benzene or methylene chloride was able to reduce the absolute viscosity by 50% for [EMIMjCl-AlCls ionic liquids with less than 50 mol% AICI3 [13]. Non-haloaluminate ionic liquids have also been studied with a range of co-solvents including water, acetone, ethanol, methanol, butanone, ethyl acetate, toluene, and acetonitrile [6,18-22]. The ionic liquid response is similar to that observed in the haloaluminate ionic liquids. The addition of as little as 20 mol% co-solvent reduced the viscosity of a [BMIM][BF4] melt by 50% [6]. 

The density of the non-haloaluminate ionic hquids is also affected by the identity of the organic cation. Like the haloaluminate ionic hquids, the density decreases as the size of the cation increases. For instance, in the non-haloaluminate ionic hquids composed of substituted imidazohum cations and the triflate anion the density decreases from 1.390 g cm for [EMIM]+ to 1.334 g cm for the [EMM(5)IM]+,... 

It must be noted that impurities in the ionic hquids can have a profound impact on the potential limits and the corresponding electrochemical window. During the synthesis of many of the non-haloaluminate ionic hquids residual halide and water may remain in the final product [30]. Hahde ions (Cl, Br, I ) are more easily oxidized than the fluorine-containing anions used in most non-haloaliuninate ionic liquids. Consequently, the observed anodic potential limit could be appreciably reduced if significant concentrations of hahde ions are present. 

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