Abstract
The oxidation of (Cl)(H2O)IrTPP with atmospheric oxygen in the presence of concentrated H2SO4 accompanied by coordination of molecular O2 and substitution of axial ligands was studied spectrophotometrically. In 16.785–18.09 М H2SO4 at 298–318 K, (Cl)(H2O)IrTPP experienced two single-electron oxidations in sequence: with an increase in the oxidation state of the iridium cation and with formation of the π-radical cation form (HSO4)IrIVTPP•+ oxidized at the aromatic ligand (k 298 = 7.2 × 10–6 mol–1 L s–1). Referring to the literature data on the oxidation of (Cl)(H2O)IrTPP in AcOH and CF3COOH, it was shown that the medium acidity and the nature of the axial ligands affect the electron removal site in the chemical oxidation of (Cl)(H2O)IrTPP with atmospheric oxygen in proton-donor solvents.
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Original Russian Text © E.Yu. Tyulyaeva, N.G. Bichan, E.G. Mozhzhukhina, T.N. Lomova, 2016, published in Zhurnal Fizicheskoi Khimii, 2016, Vol. 90, No. 1, pp. 28–33.
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Tyulyaeva, E.Y., Bichan, N.G., Mozhzhukhina, E.G. et al. Kinetics of the chemical oxidation of (5,10,15,20-tetraphenyl-21H,23H-porphinato)(chloro)(aqua)iridium(III). Russ. J. Phys. Chem. 90, 37–42 (2016). https://doi.org/10.1134/S0036024416010325
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DOI: https://doi.org/10.1134/S0036024416010325