Reduction in ionic liquids

De Giorgio F, Soavi F, Mastragostino M (2011) Effect of lithium ions on oxygen reduction in ionic liquid-based electrolytes. Electrochem Commun 13 1090-1093... 

The above reduction is in contrast to catalytic hydrogenation reaction, which requires high temperature and pressure and expensive platinum oxide catalyst and gives a mixture of products. In the above case (Scheme-4) the sequence of chemical reduction can be determined by careful monitoring of the reduction in ionic liquid. 

Table 7.5 Formal potential of the H IHAn couple and peak potential ( p) for the HAn Vi H2 + An reduction in ionic liquid media...

In order to broaden the field of biocatalysis in ionic liquids, other enzyme classes have also been screened. Of special interest are oxidoreductases for the enan-tioselective reduction of prochiral ketones [40]. Formate dehydrogenase from Candida boidinii was found to be stable and active in mixtures of [MMIM][MeS04] with buffer (Entry 12) [41]. So far, however, we have not been able to find an alcohol dehydrogenase that is active in the presence of ionic liquids in order to make use of another advantage of ionic liquids that they increase the solubility of hydrophobic compounds in aqueous systems. On addition of 40 % v/v of [MMIM][MeS04] to water, for example, the solubility of acetophenone is increased from 20 mmol to 200 mmol L ... 

Harrison et c /.146,147 have used PLP (Section 4.5.2) to examine the kinetics of MMA polymerization in the ionic liquid 18 (bmimPFfi). They report a large (ca 2-fold) enhancement in Ay and a reduction in At. This property makes them interesting solvents for use in living radical polymerization (Chapter 9). Ionic liquids have been shown to be compatible with ATRP14 "1 and RAFT.I57,15S However, there are mixed reports on compatibility with NMP.1 Widespread use of ionic liquids in the context of polymerization is limited by the poor solubility of some polymers (including polystyrene) in ionic liquids. 

When the same [NiI (NHC)2] complexes are employed as alkene dimerisation catalysts in ionic liquid (IL) solvent [l-butyl-3-methylimidazolium chloride, AICI3, A-methylpyrrole (0.45 0.55 0.1)] rather than toluene, the catalysts were found to be highly active, with no evidence of decomposition. Furthermore, product distributions for each of the catalyst systems studied was surprisingly similar, indicating a common active species may have been formed in each case. It was proposed that reductive elimination of the NHC-Ni did indeed occur, as outlined in Scheme 13.8, however, the IL solvent oxidatively adds to the Ni(0) thus formed to yield a new Ni-NHC complex, 15, stabilised by the IL solvent, and able to effectively catalyse the dimerisation process (Scheme 13.9) [25-27],... 

It appeared that, we needed to limit or omit the ethyl iodide if we were going to operate the ethylene carbonylation in ionic liquids. Unfortunately, the previous literature indicated that EtI or HI (which are interconvertible) represented a critical catalyst component. Therefore, it was surprising when we found that, in iodide based ionic liquids, the Rh catalyzed carbonylation of ethylene to propionic acid was still operable at acceptable rates in the absence of ethyl iodide, as shown in Table 37.2. Further, we not only achieved acceptable rates when omitting the ethyl iodide, we also achieved the desired reduction in the levels of ethyl propionate. More importantly, when the reaction products were analyzed, there was no detectable ethyl iodide formed in situ. However, we should note that we now observed traces of ethanol which were normally undetectable in the earlier Ed containing experiments. 

Similarly, Kou et al. published the synthesis of PVP-stabilized noble-metal nanoparticles in ionic liquids BMI PF6 at room temperature [76]. The metal nanoparticles (Pt, Pd, Rh) were produced by reduction of the corresponding metal halide salts in the presence of PVP into a refluxing ethanol-water solution. After evaporation to dryness the residue was redissolved in methanol and the solution added to the ionic liquid. The methanol was then removed by evaporation to give the ionic liquid-immobilized nanoparticles. These nanoparticles were very stable. TEM ob-... 

Scheme 41.1 Reduction of anthracene and pyrene using electropositive metals in ionic liquids with HCI as the proton source.

Catalysts other than homogeneous (molecular) compounds such as nanoparticles have been used in ionic liquids. For example, iridium nanoparticles prepared from the reduction of [IrCl(cod)2] (cod = cyclooctadiene) with H2 in [bmim][PF6] catalyses the hydrogenation of a number of alkenes under bipha-sic conditions [27], The catalytic activity of these nanoparticles is significantly more effective than many molecular transition metal catalysts operating under similar conditions. 

Another example is butene dimerization catalyzed by nickel complexes in acidic chloroaluminates 14). This reaction has been performed on a continuous basis on the pilot scale by IFF (Difasol process). Relative to the industrial process involving homogeneous catalysis (Dimersol process), the overall yield in dimers is increased. Similarly, selective hydrogenation of diene can be performed in ionic liquids, because the solubility of dienes is higher than that of monoene, which is higher than that of paraffins. In the case of the Difasol process, a reduction of the volume of the reaction section by a factor of up to 40 can be achieved. This new Difasol technology enables lower dimer (e.g., octenes) production costs 14). 

Guo, S., Shi, R, Gu, Y., Yang, J., Deng, Y., Size-controllable synthesis of gold nanoparticles via carbonylation and reduction of hydrochloroauric acid with CO and H2O in ionic liquids, Chem. Lett., 34,830-831,2005. 

Also, metals have significantly different reduction potentials in ionic liquid solutions compared to water. For example the difference in reduction potential between Cr and Pt in ionic liquids may be as little as 100 mV whereas in aqueous solutions it is in excess of 2 V. One consequence of this characteristic is that alloy coatings may be prepared more readily and that it should be possible to develop many novel alloy coatings. 

One issue is that most metal complexes formed in ionic liquids are anionic and these will have a significant effect on viscosity and mass transport. The effect of metal ion concentration on reduction current will therefore not be linear. Relative Lewis acidity will affect mass transport, ionic strength and speciation and accordingly the nucleation and growth mechanism of metals would be expected to be concentration dependent. 

The only models that exist for double layer structure in ionic liquids suggest a Helmholz layer at the electrode/solution interface [103, 104], If the reduction potential is below the point of zero charge (pzc) then this would result in a layer of cations approximately 5 A thick across which most of the potential would be dropped, making it difficult to reduce an anionic metal complex. Hence, the double layer models must be incorrect. 

When Ni(II) - NHC complexes contain an alkyl, aryl, or acyl group, reductive elimination can occur, affording Ni(0) compounds and 2-mediated organoim-idazolium salts (Eq. 16). This pathway results in catalyst decomposition for reactions by Ni - NHC systems [45]. In Ni - NHC-catalyzed olefin dimerization, Cavell and Wasserscheid showed that this decomposition is inhibited when reactions are run in ionic liquids rather than more classical solvents such as toluene [46]. 

Zhao GY, Jiang T, Han BX, et al. Electrochemical reduction of supercritical carbon dioxide in ionic liquid l-n-butyl-3-methylimidazolium hexafluorophosphate. J Supercrit Fluids. 

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