Oxidation reactions, nonadiabatic electron transfer

Let us summarize the results obtained. The theory is restricted to nonadiabatic electron-transfer reactions. If only classical modes are reorganized during the transition, the rate constant for the oxidation is ... 

Nonadiabatic Electron Transfer in Oxidation-Reduction Reactions... 

Before describing experiments designed to study the nonadiabatic regime for electron transfer in oxidation-reduction reactions systematically, some systems in which electron tunnelling, in the sense that it... 

It should be noted that most of the Co(III)2=jCo(II) exchange reactions are unsatisfactorily described by the adiabatic theory. This may be attributed partly to the fact that the spin state of the complex depends on its oxidation state Co + ion possesses a high spin t gSl configuration, whereas Co + ion has a low-spin configuration. It is evident that one-electron transfer in this case must be accompanied by the transfer of one more electron from the eg level to the t2g level, or vice versa, i.e., either one of the initial complexes or the products must be in the excited state. As mentioned above, in some cases the correlation factor p (Eq. (101)) is employed for a quantitative evaluation of nonadiabaticity. 

The reversible reaction between [Ru(NH3)5(nicotinamide)] and [Ru(NH3)5(isonicotinamide)] has been investigated to yield a self-ex-change rate for all [Ru(NH3)5py] complexes of 4.7 x 10 mol" liter s Electron transfer reactions of [Ru(NH3)5py] complexes appear for the most part to follow Marcus behavior, and reasonable agreement with the thermal electron transfer rate calculated from the IT bond of [(NH3)5Ru(4,4 -bipy)-Ru(NH3)5] was found. However, in the oxidations by Fe , deviations from Marcus behavior which were found to be entropic in nature are considered to indicate a degree of nonadiabaticity in the electron transfer and a transmission coefficient of 5 X 10 was estimated. 

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