Homogeneous reaction involving components of different redox couples—II. polarographic studies of the interactions of alkali metal cations with athracene and fluoranthene dianions in N,N-dimethylformamide and acetonitrile

Abstract

The polarographic behavior of mixtures of anthracene (An), fluoranthene (Fa) and alkali metal cations in N,N-dimethylformamide (DMF) or acetonitrile (ACN) indicates that the electrogenerated dianion of the hydrocarbon reacts with the metal cation in the diffusion layer to form ion complexes. This results, in the case of sodium or lithium cations with anthracene in both DMF and ACN, in the appearance of inverted polarographic waves. In the case of other alkali metal cations (K +, Rb +), the intensity of the polarographic wave due to the reduction to the hydrocarbon dianion is simply decreased. The stoichiometries and mechanisms of the interactions are discussed. In the presence of proton donors such as water, a competing reaction for the dianion results. The polarograms are simulated by digital approximation techniques.