Abstract
The reactions between electrogenerated superoxide ion O 2 ⨪ and two benzoate esters in N, N-dimethylformamide containing tetrabutylammonium perchlorate have been investigated. By using cyclic voltammetric techniques an e.c.e. type mechanism was found to be operative; this was confirmed by controlled potential electrolysis experiments. Secondorder rate constants for nucleophilic displacement by O 2 ⨪ on p-chlorophenyl benzoate and phenyl benzoate were estimated to be 25.0±5 and 3.0±0.3 M −1 s −1 respectively by fitting potential step reduction data to i k/ i d vs. log kt working curves.
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