Out-of-Plane Distortions in Fluorinated Nitrobenzene Radical Anions

According to the data of UHF/INDO calculations of the model conformations of fluorinated nitrobenzene radical anions, rotation of the nitro group relative to the plane of the benzene ring is accompanied by a pyramidal distortion of the group, which is of pseudo-Jahn–Teller nature. The degree of structural distortions depends on the position of the fluorine atoms in the benzene ring and on the solvent, increasing from DMF to DMF–water mixtures. The values of isotropic hyperfine interaction constants are interpreted in the series of fluorinated nitrobenzene radical anions, and the effects of water content in binary mixtures of solvents are discussed.     

Synthesis of N-(5-tetrazolyl)amidines from 5-aminotetrazole and nitriles using organoboranes

Conclusions A method has been proposed for the synthesis of N-(5-tetrazolyl)amidines from 5-amino-tetrazole, nitriles, and organoboranes through boron chelate compounds, namely, dialkyl-boryl[N-(5-tetrazolyl)amidinates].Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2622–2624, November, 1987.     

Adiabatic Potential Energy Surface of the 1,2,3-Trifluorobenzene Cation-Radical

Ab initio study of the adiabatic potential energy surface (PES) for 1,2,3-trifluorobenzene cation-radical was carried out by the ROHF, UHF, MCSCF, MP2, and DFT (B3LYP) methods with the 6-31G* basis set. The PES in question is a pseudorotation surface at all calculation levels. The pseudorotation barrier height does not exceed 3.2 kcal/mol, suggesting a possibility for its manifestations in experimental EPR spectra.     

The structure of the 1-1-difluoroethylene radical anion and the factors determining the hyperfine interaction with 19F

A structure with a pyramidal -CF₂ group is shown to desribe satisfactorily hyperfine interactions in CH₂CF_$\text{2}$ radical anions within the framework of the INDO method. The factors responsible for the substantial difference in the degree of spin density delocalization on F in CH₂CF_$\text{2}$ and C₂F_$\text{4}$ are analyzed.     

Structural features of 1,3,5-trifluorobenzene radical anion,as studied by optically detected ESR spectroscopy and quantum chemistry

The ESR spectrum of 1,3,5-trifluorobenzene radical anion was obtained for the first time using optically detected ESR spectroscopy. Experimental data and results of a quantum chemical study of the potential energy surface (density functional theory B3LYP and BHHLYP methods) are indicative of fast interconversions between nonplanar conformations of this radical anion.     

Localized growth of materials from amorphous hydrogenated carbon by barrier-discharge treatment of benzene vapor-argon mixture

The possibility of a localized growth of materials from amorphous hydrogenated carbon by the barrier-discharge treatment of a benzene vapor mixture with argon has been shown. Two types of material are produced, the “columnar” black entities of ～100 μm in diameter and 2 mm in height and the “polymeric patterns” as “honeycombs” of ～ 4–6 mm diameter with a clearly defined boundary in the form of the “swell” as high as 100 μm. The structure and composition of the materials and their growth kinetics have been investigated.     

Oxidation of Cyclohexene in the Presence of Alkanes in a Barrier Discharge Plasma

The oxidation of cyclohexene mixtures with hexane, octane, decane, and cyclohexane was studied in a dielectric-barrier discharge reactor. It was shown that a decrease in the partial pressure of cyclohexene in the mixture resulted in a significant increase in the yield of cyclohexene oxide to 75%, with the composition of oxidation products being the same as in the oxidation of individual compounds. A plausible mechanism of the reaction is proposed.