Molecular-orbital and structural descriptors in theoretical investigation of electroreduction of nitrodiazoles

It is shown how a simple theoretical approach can be used for the investiga- tion of electro-organic reactions. Mononitroimidazoles and mononitropyrazoles were studied by the semiempirical MNDO-PM3 molecular orbital method. The electro- chemical reduction potentials of diazoles have been correlated with the energy of the lowest unoccupied molecular orbital (LUMO). It was found that an admirable correla- tion could be obtained by the introduction of simple structural descriptors as a correc- tion to the energy of the LUMO. The interaction of a molecule with its surrounding de- pends on electrostatic potential and on steric hindrance. Most of these steric effects are taken into account using two parameters having a very limited set of integer values. The first () is the position of a ring substituent regarding ring nitrogens, which ac- counts for the different orientations of dipole moments and for the different shape of the electrostatic potential. The second (structural) parameter () is the type of the ring, which accounts mostly for different modes of electrode approach, and for different charge polarization patterns in two diazole rings. The extended correlation with ELUMO, and , is very good, having a regression coefficient r = 0.991. The intrinsic importance of and is exemplified by their high statistical weight.