Abstract
The Ru(IV) and Os(II) complexes (PhO)2RuTPP and OsTPP were synthesized from tetraphenylporphine (H2TPP) and K2RuO4 or K2OsO4 (taken in the molar ratio of 1 : 30) in boiling phenol. The kinetics of oxidation reactions of these complexes in solutions of HOAc (acetic), H2SO4, and HOAc–H2SO4 acids was studied. It was found that in the aerated HOAc–H2SO4 mixture heated above 340 K, these complexes are oxidized with participation of different reaction sites: the Ru(IV) complex is oxidized at macrocycle to give the π-radical-cation (PhO)2RuТPP•+, while in the Os(II) complex, the metal atom is oxidized to form the Os(III) complex. In the first case, the reaction follows the activation mechanism, whereas in the second case, the activation energy of the reaction is zero.
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