Choice of the Right Supporting Electrolyte in Electrochemical Reductions: A Principal Component Analysis

We present an analysis of a set of molecular, electrical, and electronic properties for a large number of the cations of quaternary ammonium salts usually employed as supporting electrolytes in cathodic reduction reactions. The goal of the present study is to define a measure for the quality of a supporting electrolyte in terms of the yield of the reaction considered. We performed a principal component analysis using the normalized values of the properties in order to lower the number of relevant reaction coordinates and find that the integral variance of 13 properties can well be represented by three principal components. The yield of the electrochemical hydrodimerization of acrylonitrile employing different quaternary ammonium salts as supporting electrolytes was determined in a series of experiments. We found only a very weak correlation between the yield and the values of the properties but a strong correlation between the yield and the values of the most important principal component. Very similar results are obtained for two further existing systematic experimental studies of the impact of the supporting electrolyte on the yield of cathodic reductions. For all three example reactions, a supervised regression using the two most important principal components as variables yields excellent values for the coefficients of determination. For comparison, we also applied our methodology to sets of purely structure-based features that are usually employed in cheminformatics and obtained results of almost similar quality. We therefore conjecture that our methodology in combination with a small number of experiments can be used to predict the yield of a given cathodic reduction on the basis of the properties of the supporting electrolyte.