Linear free energy relationships of half-wave reduction potentials of ( E)-4-aryl-4-oxo-2-butenoic acids

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Half-wave reduction potentials of a set of twelve ( E)-4-aryl-4-oxo-2-butenoic acids obtained by direct current polarography in methanol are reported. E 1/2 is correlated with Hammett sigma values as well as with values of frontier molecular orbitals calculated at a semiempirical molecular orbital level. Constant potential electrolysis of a representative compound shows that the first polarographic wave corresponds to one-electron reduction. The isolation of the product proves reduction of the activated double bond.