Catalytic activity and stability of anionic and cationic water soluble cobalt(II) tetraarylporphyrin complexes in the oxidation of 2-mercaptoethanol by molecular oxygen

The catalytic activity and stability of anionic cobalt(II) porphyrin complexes: 5,10.15,20-tetrakis(2.6-dicloro-3-sulfonatophenyl)porphyrinatocobalt(II), 5,10,15,20-tetrakis(2,4,6-trimethyl-3,5disulfonatophenyl)porphyrinatcobalt(II) and the eationic cobalt(II) porphyrin: 5,10,15,20-tetrakis[4-(diethylmethylammonio)phenyl]porphyrinatocobalt(II) tertraiodide have been investigated in the oxidation of 2-mercaptoethanol by dioxygen. All complexes were efficient catalysts for the auto-oxidation of 2-mercaptoethanol, The cationic cobalt(II) porphyrin has been found to be the most reactive catalyst. The rate of auto-oxidation of 2-mercaptoethanol catalysed by 5.10,15.20-tetrakis(2,4,6-trimethyl-3,5disulfonatophenyl)porphyrinatocobalt(III has been found to increase with increasing the pH from 7 to 9 then decreased at higher pH. The rate constants of auto-oxidation reaction showed linear dependence on catalyst concentration and saturation kinetics in both 2-mercaptoethanol concentrations and dioxygen pressure. Anionic cobalt(II) porphyrin complexes showed higher stability than the cationic catalyst in repeat oxidation reactions. Immobilizing the anionic catalysts on ion exchange re,,in and supporting the cationic catalyst on clay mineral montmorillonite improved their stabilities towards oxidation. (c) 2005 Elsevier B.V. All rights reserved.