Tertiary tetraols of adamantane (C₁₀H₁₆, Tricyclo[3.3.1.1(3,7)]decan) have been widely used for the synthesis of highly symmetric compounds with unique physical and chemical properties. The methods for one-stage simultaneously selective, deep, and cheap oxidation of adamantane to tetraols of different structures have not yet been developed. In this research, chemically simple, cheap, and environmentally friendly reagents are used and that is the first step in this direction. The conditions, under which the impact of a hydrogen peroxide water solution on adamantane dissolved in acetonitrile results in full conversion of adamantane and formation of a total 72% mixture of its tri-, tetra-, and penta-oxygenated products, predominantly poliols, have been found. Conversion and adamantane oxidation depth are shown to depend on the ratio of components of the water-acetonitrile solution and the method of oxidizer solution introduction when using the dimer form of 1:1 dimethylglyoxime and copper dichloride complex as a catalyst. Under the conditions of mass-spectrometry ionization by electrons (70 eV), fragmentation across three C–C bonds of the molecular ions framework of adamantane tertiary alcohols Ad(OH)_n in the range n = 0–4 increases linearly with the rise of n.

During the oxidation of hydrocarbons using hydrogen peroxide solutions, the evolution of gaseous oxygen is a side and undesirable process, in which the consumption of the oxidizer is not associated with the formation of target products. Therefore, no attention is paid to the systematic study of the chemical composition of the gas and the mechanisms of its formation. Filling this gap, the authors discovered a number of new, previously unidentified, interesting facts concerning both gas evolution and the oxidation of hydrocarbons. In a 33% H₂O₂/Cu₂Cl₄·2DMG/CH₃CN system, where DMG is dimethylglyoxime (Butane-2,3-dione dioxime), and is at 50 °C, evidence of significant evolution of gaseous hydrogen, along with the evolution of gaseous oxygen was found. In the authors’ opinion, which requires additional verification, the ratio of gaseous hydrogen and oxygen in the discussed catalytic system can reach up to 1:1. The conditions in which only gaseous oxygen is formed are selected. Using a number of oxidizable hydrocarbons with the first adiabatic ionization potentials (AIPs) of a wide range of values, it was found that the first stage of such a process of evolving only gaseous oxygen was the single electron transfer from hydrogen peroxide molecules to trinuclear copper clusters with the formation, respectively, of hydrogen peroxide radical cations H₂O₂^•+ and radical anions Cu₃Cl₅^•− (AIP = 5 eV). When the conditions for the implementation of such a single electron transfer mechanism are exhausted, the channel of decomposition of hydrogen peroxide molecules into gaseous hydrogen and oxygen is switched on, which is accompanied by the transition of the system to an oscillatory mode of gas evolution. In some cases, the formation of additional amounts of gaseous products is provided by the catalytically activated decomposition of water molecules into hydrogen and oxygen after the complete consumption of hydrogen peroxide molecules in the reaction of gaseous oxygen evolution. The adiabatic electron affinity of various forms of copper molecules involved in chemical processes is calculated by the density functional theory method.

Conformationally selective rearrangement of 1,1′-bicyclobutyl radical cations to radical cations of bicyclo[3.3.0]octane and bicyclo[3.2.1]octane that occurs at 77 K via the concerted one-step mechanism in a 1% 1,1′-bicyclobutyl solution in Freon-113 irradiated with X-rays at 77 K has been detected by means of the EPR technique. The assignment of the EPR spectra has been confirmed by MNDO-UHF calculations.

The oxidation of hydrocarbons of different structures under the same conditions is an important stage in the study of the chemical properties of both the hydrocarbons themselves and the oxidation catalysts. In a 50% H₂O₂/Cu₂Cl₄·2DMG/CH₃CN system, where DMG is dimethylglyoxime (Butane-2,3-dione dioxime), at 50 °C under the same or similar conditions, we oxidized eleven RH hydrocarbons of different structures: mono-, bi- and tri-cyclic, framework and aromatic. To compare the composition of the oxidation products of these hydrocarbons, we introduced a new quantitative characteristic, “distributive oxidation depth D(O), %” and showed the effectiveness of its application. The adiabatic ionization potentials (AIP) and the vertical ionization potentials (VIP) of the molecules of eleven oxidized and related hydrocarbons were calculated using the DFT method in the B3LYP/TZVPP level of theory for comparison with experimental values and correlation with D(O). The same calculations of AIP were made for the molecules of the oxidant, solvent, DMG, related compounds and products. It is shown that component X, which determines the mechanism of oxidation of hydrocarbons RH with AIP(Exp) ≥ AIP(X) = 8.55 ± 0.03 eV, is a trans-DMG molecule. Firstly theoretically estimated experimental values of AIP(trans-DMG) = 8.53 eV and AIP(cis-DMG) = 8.27 eV.

Molecular hydrogen is the basis of hydrogen energy. It is formed and used in many fields of industry, physics, and chemistry. Molecular hydrogen is the main product formed during the gamma radiolysis of liquid cyclohexane. When studying the mechanism of molecular hydrogen formation during the gamma radiolysis of liquid cyclohexane, we found that the values of adiabatic electron affinity, one of the fundamental characteristics of atoms and molecules, had not yet been experimentally determined for hydrogen and cyclohexane molecules. Theoretical estimates of the adiabatic electron affinity of the hydrogen molecule made by other authors varied widely ([−0.3; −5.771] eV) and could not be compared with experimental values due to the absence of such data. Using DFT calculations at the PBE0/TZVPP level of theory, and a constructed correlation with experimental values of the adiabatic first ionization potential and electron affinity for a number of molecules, neutral radicals, and atoms, we estimated, for the first time, the experimental adiabatic electron affinities of hydrogen (−3.08 eV) and cyclohexane (−2.13 eV) molecules in the gas phase. When an electron is attached to a cyclohexane molecule, a cyclohexane radical anion is formed, a new, highly reactive species that has not been studied before. A new perspective on molecular hydrogen formation during the gamma radiolysis of liquid cyclohexane was introduced and discussed.

Solutions of 5-vinyl-2-norbornene (VNB, 5-vinylbicyclo[2.2.1]hept-2-ene) and the related compounds 5-ethylidene-2-norbornene (ENB, 5-ethylidenbicyclo[2.2.1]hept-2-ene) and 2-vinyl-2-norbornane (VNN, 2-vinylbicyclo[2.2.1]heptane) in cyclohexane have been irradiated with γ-rays at 40°C. The initial radiation-chemical yields G₀ for the consumption of the solutes and the formation of final products of γ-radiolysis of the solvent cyclohexane have been determined. It has been shown that solute consumption and molecular hydrogen formation yields G₀(−RH) and G₀(H₂), respectively, are linearly related to the first vertical ionization potential of the solute. The G₀ values of molecular hydrogen, cyclopentadiene (CPD), butadiene, and methylallene, minor products of γ-radiolysis (40°C) of liquid VNB, ENB, and dicyclopentadiene (tricyclo[5.2.1.0^2.6]decadiene-3.8), have been determined. It has been shown that the G₀ values of CPD formation linearly depend on the first vertical ionization potentials of γ-irradiated bicyclic dienes. It is concluded that the γ-irradiation of cyclohexane generates two kinds of radical cations, which differ in mobility and reactivity.