Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases p. 3215 - 3232 (1986)
Update date:2022-08-29
Topics:
Harriman, Anthony
Christensen, Paul A.
Porter, George
Morehouse, Kim
Neta, Pedatsur
Richoux, Marie-Claude
Manganese(III) porphyrins (Mn(III)P) are easily oxidised to the corresponding Mn(IV)P in alkaline aqueous solution.At pH<5 the oxidation product is a Mn(III)P ?-radical cation.These oxidised metalloporphyrins have limited stability in water and they revert to the original Mn(III)P upon standing in the dark.The rate and mechanism of this inherent reduction process depends upon pH, with lower pH giving the higher rates.The inherent reduction appears to involve disproportionation and rearrangement of the Mn(IV)P but it does not lead to formation of molecular O2.Addition of colloidal RuO2*2H2O, a good O2-envolving catalyst, has a pronounced effect upon the reduction process.The oxidised metalloporphyrin is bound to the catalyst particles by electrostatic forces, and at pH<11 the bound material decays more slowly than the free compound.For 8
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