Cyclic voltammetric and EPR spectroscopic studies on apical substituent effects in radical anions of 9-substituted and 9,10-disubstituted nitroethanoanthracenes

Cyclic voltammetry and electron paramagnetic resonance spectroscopy were used to examine apical substituent effects on the properties of Me(2)SO solutions of the radical anions from g-substituted and 9,10-disubstituted 2- and 3-nitro-9,10-dihydro-9,10-ethanoanthracenes dagger (1)-(24). The reductions of the nitro group are, in general, reversible at 100 mV s(-1) and at 20 degrees, except where there are coupled intra- or inter-molecular electron or proton transfer reactions with aliphatic bridgehead substituents, such as a carboxylic acid or iodine. The substituent effects for the meta- and para-nitroethanoanthracene systems are both similar and additive. This similarity in the meta and para polar substituent effects is attributed to the orthogonality of the pi*(ArNO2/ArNO2-) orbital with the sigma* orbital of the carbon substituent (C-X) groups at the bridgehead positions. Overall, the meta substituent effect was slightly lower than that for corresponding simple meta-nitrobenzyl systems, but the para-nitro systems showed substituent effects that are a factor of 2 smaller than that for corresponding simple para-nitrobenzyl systems. These linear correlations between the substituent effects and redox potentials have been used to estimate the redox potentials of irreversible systems, which are required for digital simulations of reactions involving nitroaryl radical anions. Only small substituent effects are present in hyperfine coupling with the aliphatic and aromatic protons of the nitroaromatic radical anions of ethanoanthracenes (1)-(13), but a clear trend to lower nitrogen hyperfine values was observed with increasing electron-withdrawing ability of the apical substituent. In addition, no spin density was transferred to the benzylic bridgehead substituent in any of the nitro radical anions studied, clearly demonstrating that the bond between the bridgehead substituent and the carbon at a benzylic position is orthogonal to the pi-system of the nitroaromatic ring bearing the odd electron.