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On the origin of voltammetric pre-peaks and cathodic potential shifts during anodic substitution reactions

1973; Elsevier BV; Volume: 18; Issue: 9 Linguagem: Inglês

10.1016/0013-4686(73)80078-7

1873-3859

Bo Svensmark, Vernon D. Parker,

Photochemistry and Electron Transfer Studies

During voltammetric pyridination of 9-phenylanthracene a pre-peak was observed, the height of which was in direct relation to the stoichiometric ratio of 9-phenylanthracene and pyridine. In order to determine whether or not the latter result could be taken as evidence for a nucleophile assisted electron transfer, a “non-assisted” mechanism was simulated. It was found that an ecec mechanism gave substantial cathodic shifts of the peak potential for oxidation of a substrate in presence of a reactant, and if the rate constants were sufficiently high not only a cathodic shift, but also a pre-peak was observed during simulation. Thus, the experimental observations cannot be used as evidence for an assisted mechanism.