Abstract
Effect of modification of the axial (fifth and sixth) coordination sites on the physicochemical properties and reactivity of iridium(III) complexes with 5,10,15,20-tetraphenyl-21H,23H-porphine was studied. Oxidation reactions of (Cl)(H2O)IrTPP in protic solvents by atmospheric oxygen (on assistance of protons at high concentration) preceded by ligand substitution at the axial position were studied. It was found that (Cl)(H2O)IrTPP in 100% AcOH undergoes slow one-electron oxidation at the aromatic ligand to form π cation radical (CH3COO)(CH3COOH)IrTPP·+. The reaction was studied in 100% AcOH (H2O content 0.078%) at 288–308 K, its kinetic parameters were obtained. The (Cl)(H2O)IrTPP reaction product in CF3COOH was identified as complex (CF3COO)2IrIVTPP oxidized at the central metal cation. It was experimentally confirmed that the reaction in 99% CF3COOH at 298 K proceeds in two stages: the substitution of axial Cl− and H2O by excess CF3COO− (k eff = (1.8 ± 0.1) × 10−3 s−1) and the oxidation of iridium to Ir(IV) (k eff = (8.0 ± 0.5) × 10−5 s−1). Data on similar Re(III) complexes (PhO)ReTPP and (Cl)ReTPP are presented for comparison.
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Original Russian Text © E.Yu. Tyulyaeva, E.G. Mozhzhukhina, N.G. Bichan, T.N. Lomova, 2015, published in Zhurnal Neorganicheskoi Khimii, 2015, Vol. 60, No. 2, pp. 194–202.
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Tyulyaeva, E.Y., Mozhzhukhina, E.G., Bichan, N.G. et al. Chemical structure and reactions of axially coordinated iridium(III) porphyrins. Russ. J. Inorg. Chem. 60, 157–165 (2015). https://doi.org/10.1134/S0036023615020199
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DOI: https://doi.org/10.1134/S0036023615020199