AcidBase and Coordination Properties of Some
Palladium(II)Porphyrins

E. Yu. Tyulyaeva, O. V. Kosareva, M. E. Klyueva, and T. N. Lomova

Institute of Solution Chemistry, Ivanovo, Russia

Received July 5, 2007

Abstract—The speciation and reactions of palladium(II) complexes with meso-tetraphenylporphine (H₂TPP)
and meso-tetraphenyl--octaethylporphine (H₂TetPOEP) were studied in H₂SO₄H₂O and H₂SO₄HOAc protic
solvents. H-associated species of PdTPP and PdTetPOEP were found to exist in sulfuric acid with concentra-
tions of 16.33–17.38 and 17.48–18.22 mol/L, respectively. The kinetics of one-electron oxidation of complexes
in the coordinated aromatic macrocycle were studied. A third-order rate equation was determined, and the
mechanism of the oxidation reaction was substantiated with kinetically significant stages of dioxygen coordi-
nation, electron transfer from the macrocyclic aromatic system to dioxygen, and H-association equilibrium
between the complex and sulfuric acid. The effects of peripheral ethyl substituents in the macrocyclic ligand on
the reactivity of palladium(II)porphyrins were revealed.

DOI: 10.1134/S0036023608090106

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