EE Mechanism and Comproportionation

Given that - f b/c means that the comproportionation step will be highly favourable, since in this case Keq 1. 

The reduction of[ r] — C6Me6)2Ru][Bp4]2 is known to be a two-electron process in acetonitrile with 0.5 M BU4NPF6 at a platinum electrode. Simulated voltammetry for this system is depicted in Fig. 7.1 the values for this simulation were taken from D.T. Pierce and W.E. Geiger [/. Am. Chem. Soc. Ill (1989) 7636]. At low scan rates, 

This experiment is significant for two reasons. First, it provides direct evidence that the electron transfer should be viewed as occurring in two discrete steps, and not in a concerted manner. 

C6Me6)2Ru - Peak 0x2 corresponds to the two-electron oxidation of the neutral species, () —C6Me6)( —C6Me6)Ru, to the dication. In the absence of a chemical step during the forward scan, all of the electroactive material at the electrode has been reduced to the neutral species, and hence no peak is observed at 0x1. It is not until 0x2 that the oxidation of the neutral species may occur due to the overpotential associated with the slow oxidation of (jj -C6Me6)(j -C6Me6)Ru to (jj -C6Me6)2Ru+. 

In the case where this reaction occurs, the concentration of (—C6Me6)2Ru becomes non-zero, and hence a peak is observed at 0x1. 

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