Electronic structure of molecules of diphenyl bridge compounds

Using the CNDO/2 method, we have calculated the valence electron density distribution in molecules of diphenylamine and its 13 derivatives with the substituents COOH, NO₂, OCH₃ on the aromatic rings of ionized forms of some diaryl amines, and also 4-amino- and 4-amino-4-adnitro substituted compounds with bridge groups NH, O, S, CH₂, CH=CH and analogous diphenyl derivatives. We have shown that independently of the nature of the bridge group, the principle of uncoupling of the aromatic rings is basically retained. Strong long-range effects of the substitutents along the chain of chemical bonds are not apparent. We have calculated the electrostatic molecular potential of the indicated compounds. We have established correlations between the electrostatic molecular potential and the protonization constants, the oxidation-reduction potentials of diarylamines; and also between the electrostatic molecular potential and the reaction rate constant for acylation of primary bridged amines at the amino group.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 21, No. 1, pp. 84–88, January–February, 1985.