Substituent,solvent and steric effects on the electrochemical reduction of aziridinium salts |
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Authors: | Delanson R. Crist Arnold P. Borsetti Mary Beth Kass |
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Abstract: | The polarographic behavior of a series of N,N-dimethyl-2-arylaziridinium fluorosulfonates was investigated as another example of ring-opening reactions of this important class of compounds. Half-wave potentials showed that in water reduction was facilitated by electron-donating groups. This unusual result was explained in terms of electron transfer to an aminocarbonium ion-like species. In methylene chloride, however, two one-electron waves were observed, with the first showing a normal substituent effect (? = 0.17 ± 0.03 V). This result indicated direct electron transfer to the aziridinium ion itself to form a radical species which was detected by cyclic voltammetry. Reasons for the change in mechanism are presented, and E1/2 values for selected aziridinium salts illustrate the importance of steric effects on the reduction process. |
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