Alkali metal ionic liquids

Ogihara, W. et al., Ionic conductivity of polymer gels deriving from alkali metal ionic liquids and negatively charged polyelectrolytes, Electrochim. Acta, 49,1797,... 

A series of polymer gels derived from alkali metal ionic liquids and negatively charged polyelectrolytes were studied for their ion transport properties. The conductivity observed was mostly in the range of 10 to 10" S/cm at room temperature. The gels showed a decrease in conductivity with increasing polymer fraction. 

Reactions with Protic, ionic, Poiar Reagents. The reactions of radical anions with proton donors include the reduction of arenes, the well-known Birch reduction, as well as alkynes by alkali metals in liquid ammonia. Both reactions have synthetic utility and belong to the few radical ion reactions included in elementary textbooks. 

It should also be noted that some nonradical ionic and condensation reactions of monomers with cellulose are used to modify the properties of cellulosic products. In one type of anionic-initiated reaction of monomers, cellulose is reacted with concentrated aqueous solutions of alkali metal hydroxides to yield cellulose copolymer. Free alkali metal in liquid ammonia or alkali metal alkoxides in nonaqueous systems may also be used as initiators of cellulose alkoxide derivatives. In cationic-initiated formation of copolymers, cellulose is reacted with an acid, such as boron trifluoride, to yield a cellulosic carbonium ion which initiates reactions with vinyl monomers. Condensation reactions of cyclic monomers with cellulose also form copolymers. Cellulose is usually slightly oxidized and also has reactive hydroxyl groups on carbons C-2, C-3 and C-6 of the anhydroglucose unit. The reactions of cyclic monomers are initiated at these carbonyl groups. A heating step may increase cellulosic oxidation and thereby increase the yield of these condensation products of cellulose and cyclic monomers." ... 

In the meantime, we believe that the best prediction of the toxicity of an ionic liquid of type [cation] [anion] can be derived from the often well known toxicity data for the salts [cation]Cl and Na[anion]. Since almost all chemistry in nature takes place in aqueous media, the ions of the ionic liquid can be assumed to be present in dissociated form. Therefore, a reliable prediction of ionic liquids HSE data should be possible from a combination of the loiown effects of the alkali metal and chloride salts. Already from these, very preliminary, studies, it is clear that HSE considerations will be an important criterion in selection and exclusion of specific ionic liquid candidates for future large-scale, technical applications. 

Ionic LCs are interesting systems because they combine the properties of LCs with those of ionic liquids. Although alkali metal soaps were among the first thermotropic LCs to be systematically studied, ionic liquid crystalline derivatives have been reported less frequently than those based on neutral molecular and macromolecular species [39]. When the halide of [AuX(CNR)] complexes is substituted by a second isocyanide, ionic complexes [Au(CNR)2][Y] [R = C6H40C H2 + i (27a),... 

Recently, there has been considerable interest in developing molten salts that are less air and moisture sensitive. Melts such as l-methyl-3-butylimidazolium hexa-fluorophosphate [211], l-ethyl-3-methylimidazolium trifluoromethanesulfonate [212], and l-ethyl-3-methylimidazolium tetrafluoroborate [213] are reported to be hydro-phobic and stable under environmental conditions. In some cases, metal deposition from these electrolytes has been explored [214]. They possess a wide potential window and sufficient ionic conductivity to be considered for many electrochemical applications. Of course if one wishes to take advantage of their potential air stability, one loses the opportunity to work with the alkali and reactive metals. Further, since these ionic liquids are neutral and lack the adjustable Lewis acidity common to the chloroaluminates, the solubility of transition metal salts into these electrolytes may be limited. On a positive note, these electrolytes are significantly different from the chloroaluminates in that the supporting electrolyte is not intended to be electroactive. 

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