Electron Transfer Reactions
The most important theoretical ideas concerning adiabatic outer sphere electron transfer reactions in solution are summarized. The kinetics of the reduction of a series of different tris-1,10,-phenanthroline complexes of Fe (III) by Fe (CN) 6 4- were measured in order to test the influence of the redox-potential on these reactions. The electron exchange rate of the complexes Fe(dipy) 3 3+ , Ru(dipy) 3 3+ and Os(dipy) 3 3+ was derived from the study of their reduction by Fe(CN) 6 4- . Using the redox reaction between the anionic complexes of Fe(CN) 6 4- and IrCl 6 2- the effect of added cations was investigated. It was observed that the cations not only shield the coulombic interaction but also exert an additional accelerating effect, which increases in the order Li+, Na+, K+, NH 4 + , Rb+ and Cs+. Monovalent cations with an ionic radius of 0.23 nm were found to cause the maximum rate enhancement.
KeywordsElectron Transfer Reaction Outer Sphere Reorganization Energy Transition State Theory Observe Rate Constant
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