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

The intramolecular electron transfer reaction within the binuclear complex [(en)(2)Co-III(mu -2-pzCO(2))Fe-II(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 reorganizati on free energy and the reaction free energy were obtained. This has permitt ed us to establish that, in spite of the similar behaviour observed for k(e t) in both kinds of micellar solutions, in the case of SDS solutions the ki netics is controlled by both the driving force and the reorganization energ y. In the case of CTACl, only the reorganization energy controls the k(et) variations. (C) 2001 Elsevier Science B.V. All rights reserved.