Esr and polarography of nitroazoles. 4. Polarographic study of nitrobenzimidazoles

The electrochemical reduction of 2-substituted 5(6)-benzimidazoles has been studied with the aid of classical polarography and cyclic voltammetry in acetonitrile. The influence of the substituents in position 2 on the magnitudes of the half-wave potentials of the first stage is exerted by induction and resonance mechanisms with approximately the same contributions, and that on the magnitudes of the half-wave potentials of the second stage predominantly by the resonance mechanism. The possibilities of taking the radical-stabilizing factor into account in the correlations are discussed. In order to study the 2-substituted 5(6)-nitrobenzimidazole series, their pK _a values in acetonitrile have been determined by potentiometric titration.For communication 3, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1246–1251, September, 1984.     

Mass-spectrometric study of the cyclization of diazo ketones. 2. Cyclization of 1-diazo-4-sulfonylaminobutan-2-ones to N-sulfonylpyrrolidin-3-ones

A comparison of the mass spectra of 1-diazo-4-sulfonylamino-butan-2-ones and N-sulfonylpyrrolidin-3-ones makes it possible to conclude that under the conditions of electron impact and chemical ionization the molecular ions of the investigated diazo ketones lose a molecule of nitrogen and undergo partial cyclization to the corresponding pyrrolidinones without undergoing the Wolff rearrangement.See [1] for Communication 1.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 919–925, July, 1982.     

The mutual influence of ligands in transition metal bis-chelates

Electronic structure quantum chemical calculations of the Fe(II), Ni(II) and Cu(II) bis-chelate series are reported. The nature of the ligand mutual influence effect on these compounds is elucidated. This effect manifests itself in polarization of metal—ligand bonds. The ligands which have highly covalent bonds with the metal form bonds of even greater covalent character in mixed complexes, whereas bonds for the other ligands become more ionic.     

Electronic regioselectivity in the reactions of pyridinium ylides with tetracyanoethylene

Highly regioselective reactions of pyridinium ylides with tetracyanoethylene occur via an Ad_N-E mechanism to form Z-isomers of 3-aroyl-3-(1-pyridinio)-1,1,2-tricyano-2-propenides-1, corresponding in structure to 1,4-ylides with maximum charge separation. If the unsaturated nitrite starting material contains a nucleofugal group 1,2-elimination predominates over 1,3-elimination.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1087–1094, August, 1991.