Abstract
The oxidation of the acetate anion mediated by tris(4-bromophenyl)ammoniumyl, electrogenerated from the parent amine, has been investigated using ESR with an in situ channel electrode flow cell. In the absence of acetate, the oxidation of tris(4-bromophenyl)amine (TBA) is a reversible one-electron process which forms the corresponding radical cation, tris(4-bromophenyl)ammoniumyl (TBA˙+). In the presence of acetate the process takes on the characteristics of the catalytic (EC′) mechanism. Analysis of the diffusion-limited current/electrolyte flow rate and ESR signal/current/electrolyte flow rate behaviour allows the precise mechanism to be deduced. This is shown to be an EC′ pre-equilibrium mechanism: TBA – e → TBA˙+, TBA˙++ CH3CO–2⇌ TBA + CH3CO˙2, CH3CO˙2→ CH˙3+ CO2 with rate-determining electron transfer between the amine radical cation and the acetate anion.
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