Electron transfer reactions in micellar systems: Separation of the true (unimolecular) electron transfer rate constant in its components Original Research Article

The intramolecular electron transfer reaction within the binuclear complex [(en)2CoIII(μ-2-pzCO2)FeII(CN)5]− has been studied in micellar (dodecylsulphate sodium salt (SDS) and hexadecyltrimethylammonium chloride (CTACl)) solutions. The true (unimolecular) electron transfer rate constant as well as the parameters controlling this rate constant, the reorganization free energy and the reaction free energy were obtained. This has permitted us to establish that, in spite of the similar behaviour observed for ket in both kinds of micellar solutions, in the case of SDS solutions the kinetics is controlled by both the driving force and the reorganization energy. In the case of CTACl, only the reorganization energy controls the ket variations.