Journal of Physical Chemistry p. 2462 - 2468 (1986)
Update date:2022-07-31
Topics:
Richoux, M. C.
Neta, P.
Harriman, Anthony
Baral, S.
Hambright, P.
One- and two-electron reduction products of several metalloporphyrins have been studied by steady-state and pulse radiolysis in aqueous and methanolic slutions and by photochemistry and electrochemistry in aqueous solutions.This study concentrates on the TMPyP (tetrakis(N-methyl-4-pyridyl)porphyrin) complexes of GaIII, GeIV, and InIII, and the TPyP (tetra(3-pyridyl)porphyrin) complex of SbV, and compares them with the previously studied complexes of ZnII, AlIII, and SnIV.All these porphyrins undergo one-electron reduction on the ligand to form ?-radical anions.The rates of formation and decay of these species have been studied under various conditions.The lifetimes of these radicals were found to vary greatly; those of SbV and SnIV are completely stable while some others decay in the millisecond range.The stability decreases in the order SbV, SnIV, InIII, GeIV, GaIII, AlIII, ZnII, which was found to correspond to the order of the porphyrin ring reduction potentials determined under similar conditions.Increased lifetime of the radical upon increase in electronegativity of the metal was found to be due to inhibition of porphyrin ring protonation, which is a necessary step in the formation of final products.The final two-electron reduction products are mainly phlorin anions.The same products were observed upon photochemical reduction.The potentials for the first and second one-electron reduction of the porphyrins were determined by cyclic voltammetry.The separation between the first and second wave gives an indication of the stability of the ?-radical anion.
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