A correlation of half-wave reduction potentials with theoretical calculations for some nitrogen-containing heteromolecules in dimethylformamide

Abstract

Half-wave reduction potentials have been measured for 35 unsubstituted and 19 methyl-substituted heteromolecules. An attempt is made at correlating the first half-wave reduction potentials of the unsubstituted heteromolecules against the simple Huckel m_{m+ 1} eigenvalues for the lowest unoccupied energy level, a value of h for nitrogen (α_N=α_C+h_Nβ) being derived from perturbation theory. Methyl-substituted heteromolecules have been investigated by use of several different ‘models’ for the methyl group. Finally an estimation of the electron affinities and differences in solvation energies is given in an attempt to improve the correlation. It appears that solvation-energy terms are no more critical than for the corresponding aromatic hydrocarbons.