Electrochemical and ESR study of the CH bond activation. Electrocatalytical oxidation with participation of radical cation of phenazine-di-N-oxide

Electrochemical and Electron Paramagnetic Resonance Study of the Mechanism of Oxidation of Phenazine-di-N-oxide in the Presence of Isopropyl alcohol at Glassy Carbon and Single-Walled Carbon Nanotube Electrodes

“…The detection of the same intermediate in CH 3 OH and CH 3 OD indicated that CH 3 group of alcohol was involved in formation of the intermediate. To explain the results obtained in [1][2][3][4][5][6][7][8], the E 1 C 1 E 2 C 2 mechanism of two-stage electrode process characterized by catalytic current at the second electrode stage was suggested. The overall two-electron catalytic oxidation of the organic substance in complex with aromatic di-Noxide radical cation was assumed to occur.…”

“…Previously, it was found [1][2][3][4][5][6][7][8] that electrochemically generated aromatic di-N-oxide radical cations are carriers of active oxygen that is capable of activating the C-H bond of the substrate. The mechanism of the oxidation of phenazine-di-N-oxide (PhenDNO), pyrazine-di-N-oxide, and its substituted derivatives in the presence of organic compounds (alcohols, ethers, cyclohexane) was studied by cyclic voltammetry [1][2][3][4][5][6][7][8].…”

“…The mechanism of the oxidation of phenazine-di-N-oxide (PhenDNO), pyrazine-di-N-oxide, and its substituted derivatives in the presence of organic compounds (alcohols, ethers, cyclohexane) was studied by cyclic voltammetry [1][2][3][4][5][6][7][8]. In the study of the oxidation of PhenDNO in methanol and its deuterated derivatives CH 3 OD and CD 3 OD by EPR electrolysis [3], EPR spectra of radical intermediates were recorded with g-factor of 2.0023 in CH 3 OH and CH 3 OD and 2.0023 and 2.0036 in CD 3 OD. It was assumed that the radical intermediates were complexes of radical cation PhenDNO +• with methanol and its deuterated derivatives.…”

Energetics of the N−O Bonds in 2-Hydroxyphenazine-di-N-oxide

“…16 The mechanism of oxidation of organic substrates in the presence of a mediator, the electrochemically generated radical cation of phenazine-di-N-oxide, has been studied by ESR electrolysis and cyclic voltammetry. For di-N-oxides, such as phenazine-di-N-oxide, a new overall two-electron mechanism of electrocatalytical oxidation of substrate, via formation of the complex of substrate with radical cation of aromatic di-N-oxide, has been proposed.…”

“…For di-N-oxides, such as phenazine-di-N-oxide, a new overall two-electron mechanism of electrocatalytical oxidation of substrate, via formation of the complex of substrate with radical cation of aromatic di-N-oxide, has been proposed. 16 The importance of the (N-O) bonds for selective activity raises an increasing interest in the thermochemical study of new heteropolycyclic species, as well as their N-oxide derivatives, to explore their energetic properties. Thermochemical data for phenazine-di-N-oxide derivatives continue to be relatively scarce.…”