A combination of in situ ESR and in situ NMR spectroelectrochemistry for mechanistic studies of electrode reactions: the case of p-benzoquinone.

A combined in situ NMR and in situ ESR spectroelectrochemical study of a reaction mechanism is presented detecting and describing the whole number of paramagnetic and diamagnetic intermediates and final products in an electrode reaction. While in situ NMR spectroelectrochemistry provides a powerful method for the study of structural or electronic changes of diamagnetic molecules in any electrochemical reaction mechanism, in situ ESR spectroelectrochemistry is the method of choice to detect paramagnetic structures and to characterise their electronic state via the g-value and hyperfine splitting in redox reactions. To demonstrate the power of this combination of magnetic spectroscopies in electrochemistry, the reduction of p-benzoquinone to hydroquinone is followed by both these spectroelectrochemical methods at selected pH values, thus considering the influence of the proton on the reaction mechanism. The results of both in situ spectroelectrochemical methods at the same redox system are used to get the complete reaction mechanism of p-benzoquinone at electrodes in aqueous solutions.