AbstractThe polarographic reduction potentials of a series of aromatic sulfones and homologous alkyl tosylates in anhydrous NN‐dimethylformamide have been measured. The relation between reduction potential and structure is discussed on the basis of HMO. calculations, under the assumption that compounds PhSO2X (X = NR1R2, OR, halogens) are sulfone derivatives A critical approach is made of the use of theTaft‐Hammettrelation for correlating half‐wave potentials. The different reduction mechanisms at the electrode observed in aprotic and protic media for the above compounds are satisfactorily accounted for by simple MO. calcula