Four different ionic liquids, based on 1-alkyl-3-methylimidazolium or quaternary ammonium cations, were
used as reaction media for several typical electrochemical reactions with a strict control of the residual water
concentration. The oxidation of organic molecules (anthracene, naphthalene, durene, 1,4-dithiafulvene, and
veratrole) for which the cation radicals undergo first and second-order kinetics reactions were investigated in
ionic liquids and compared with their behavior in acetonitrile. From the analysis of the voltammetric current
responses, the reaction mechanism was established and the thermodynamic and kinetics parameters were
extracted. The most interesting result is that the nature of investigated mechanisms is almost unchanged in
ionic liquids as compared with conventional organic media. A decrease of the electron-transfer kinetics from
the aromatic molecules to the electrode (around 1 order of magnitude) is observed for all of the studied
molecules, indicating an higher solvent reorganization during the charge transfer. The kinetics of the chemical
reactions triggered by the electron transfer are slightly affected by the use of ionic liquid. The only noticeable
effect is a decrease of the bimolecular reactions rates partly due to a lowering of the limiting diffusion-controlled kinetics rate constant together with a specific solvation effect of reactants in these special media.
These preliminary electrochemical experiments appear as encouraging results for the use of ionic liquids in
a “green” electrochemistry.
Soluble Candida antarctica lipase B dissolved in ionic liquids showed good synthetic activity, enantioselectivity and operational stability in supercritical carbon dioxide for both butyl butyrate synthesis and the kinetic resolution of 1-phenylethanol processes by transesterification.
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