Chemical Properties of Water-soluble Porphyrins 3. The Reaction of Superoxide Radicals with Some Metalloporphyrins

Summary

The catalytic efficiency of some water soluble metalloporphyrins upon the disproportionation of the superoxide radicals has been determined by observing the rate of decay of the radical at 254 nm. The Fe(III), Mn(III), Co(III), Ni(II), Cu(II) and Zn(II) derivatives of tetrakis-(4-N-methylpyridyl) porphyrin (TMPyP), tetra(4-N,N,N-trimethylanilinium) porphyrin (TAP), and tetra(4-sulphonatophenyl) porphyrin (TPPS₄) were studied. The order of catalytic efficiency found was Fe(III)TMPyP > Mn(III)TMPyP > Co(III)TMPyP ≅ Mn(TAP) > Fe(III)TPPS₄. Other metalloporphyrins did not show catalytic activity. Reduction potentials of the catalytically active metalloporphyrins determined from cyclic voltamograms indicate the importance of having a second energetically accessible oxidation state available to the metal ion for catalysis. The catalytic action of the above metalloporphyrins is discussed in terms of inner and outer-sphere mechanisms. It is suggested that with the exception of Fe(III)TMPyP which reacts via an inner-sphere mechanism, the others are governed by an outer-sphere mechanism.