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We observed for the first time the reaction of oxidation of ferric xylenol orange chelates by hydrogen peroxide in aqueous solution. The reaction is accompanied with decoloration of the violet aqueous solution. Based on generally accepted conception, there is a process of free radical chain oxidation of indicator molecule in the solution. However, after investigating the final colorless solution by 1H NMR-spectroscopy we found the modified but not broken structure in which the initial hydrocarbon core remained mainly unchanged. We concluded that kind of reaction was an oxyfunctionalization by hydrogen peroxide versus free radical chain destruction. We argued steps of the reaction such as N-oxidation, Cope’s elimination, and certain rearrangements with possible products oligomerization. There was a need to explain the mechanism of interaction between the ferric iron ion and the hydrogen peroxide molecule and to argue the nature of intermediate reactive oxygen species. There is similarity between the ferric-catalyzed hydroperoxide xylenol orange oxidation and the peroxygenase-catalyzed biochemical oxyfunctionalization reactions. However, based on literature data and molecular orbital modeling, we proposed another mechanism of interaction between the ferric iron ion and the hydrogen peroxide molecule instead the tetravalent iron generation. Concretely, we proposed the hydrogen peroxide zwitter-ionization (isomerization to oxywater molecule) and subsequent intramolecular disproportionation with generation of a water molecule and a singlet oxygen atom as a reactive oxygen species. In this view, the iron ion oxidation state is unchanged during the reaction and remains ferric. An oxyfunctionalization of any organic substrate by hydrogen peroxide in the presence of ferric iron ions is promising approach in organic synthesis. However, the usage of organic ligands for ferric iron ions as components of catalysts is limited and requires only non-oxidizable compounds. On the other hand, one can choose an oxidation substrate as a ligand for ferric iron ions that is the formation of chelate complex of ferric catalyst with an organic substrate.Forcitation:Chumakov A.A., Kotelnikov O.A., Slizhov Yu.G. Oxidation of ferric xylenol orange chelates by hydrogen peroxide in aqueous solution: conception of oxygen singlet atoms generation from hydrogen peroxide. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 2018. V. 61. N 2. P. 15-22

Gas chromatographic sorbents based on Siloсhrome S-80 adsorptively modified with 8-hydroxyquinolinate, 1-phenylazo-2-naphtholate and 2-nitroso-1-naphtholate of nickel(II) have been obtained. It has been established that the thermal stability (up to 170–350 °C) of chelate-containing sorbents is sufficient for carrying out gas chromatographic separations. The IR and Raman spectra of the obtained materials confirmed the success of the complexation processes in the synthesis of complex nickel(II) compounds and the retention of coordination bonds after the deposition of chelates on silica gel. The characteristics of the surface and the porous structure of the prepared sorbents are investigated. As a result of adsorptive modification of Silochrome S-80 with nickel(II) chelates, it’s specific surface area (84 m2/g) decreases by 12–32 m2/g along with a decrease in the average pore size, which indicates the fixation of modifiers at the edges of large pores. It was shown that modification of Silochrome S-80 with 8-hydroxyquinolinate, 1-phenylazo-2-naphtholate, 2-nitroso-1-naphtholate of nickel(II) has a significant effect on the chromatographic polarity and selectivity of sorbents. The presence of a polar nitroso-groups in the composition of nickel(II) 2-nitroso-1-naphtholate makes the metal center more accessible for donor-acceptor interactions with sorbates (pyridine, carbonyl compounds). Also, the nitroso-group is active in the formation of hydrogen bonds with alcohols, which complicates their elution at column temperatures below 170 °C. The greatest affinity to the homologous of arenes is shown by silochrome modified by a nickel(II) complex with the least bulky 8-hydroxyquinolinate ligands, which leads to an increase in the retention times of aromatic and polyaromatic compounds along with an increase of the sorbent selectivity. The possibility of practical application of a chromatographic column filled with Silochrome S-80 with deposited nickel(II) 8-hydroxyquinolinate for gas chromatographic (FID) separation of mixtures of polyaromatic compounds in the temperature programming mode is shown.

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