Integrated Study of the Thiocyanate Anion Electrooxidation by Electroanalytical and Computational Methods

The mechanism of the electrochemical oxidation of thiocyanate anion in acetonitrile was studied by cyclic voltammetry, chronoamperometry, electrolysis, digital simulations and quantum chemical calculations. The experimental data indicated the complex character of the reaction mechanism, which includes reactions of thiocyanate anion with the products of its oxidation, thiocyanate radical and thiocyanogen. It was proposed that the last reaction takes place in the reduction of thiocyanogen as well. The DFT PCM-SMD M06–2X/aug-cc-pVQZ calculations show that the reaction of thiocyanate anion with thiocyanate radical • and disproportionation of thiocyanogen anion radical are thermodynamically favorable. The effects of the mentioned reactions on the shape of the curves of cyclic voltammetry and chronoamperometry as well as that of the mass transfer regime are discussed.

Examining the Influence of Anion Nucleophilicity on the Polymerisation Initiation Mechanism of Phenyl Glycidyl Ether

The reaction of phenyl glycidyl ether (PGE) with 1‐ethyl‐3‐methylimidazolium acetateand 1‐ethyl‐3‐methylimidazolium thiocyanate to initiate the polyetherification reaction wasexamined using thermal and spectral analysis techniques. The influence of the nucleophilicity of theanions on the deprotonation of the 1‐ethyl‐3‐methylimidazolium cation determined the reactionpathway. The thermal degradation of the ionic liquid liberated the acetate ion and led, subsequently,to the deprotonation of the acidic proton in the imidazole ring. Thus, polymerisation of PGEoccurred via a carbene intermediate. The more nucleophilic thiocyanate anion was not sufficientlybasic to deprotonate the 1‐ethyl‐3‐methylimidazolium cation, and thus proceeded through directreaction with the PGE, unless the temperature was elevated and a competing carbene mechanismensued.