In situ FTIR spectroelectrochemistry and spectral simulations using DFT: Efficient complementary tools to elucidate complex electrochemical mechanisms

In situ infrared spectroelectrochemistry has been used to reinvestigate the electrochemical oxidation of N,N-dimethylaniline in acetonitrile. The addition of a proton scavenger having a specific spectroscopic signature, permits to verify the mechanism leading to the formation of the dimer N,N,N′,N′-tetramethylbenzidine (TMB). Peaks characteristic of TMB and of its oxidation products have been experimentally identified and verified by using DFT calculations.