A water-soluble chromium porphyrin, [Cr(111)TF(4)TMAP](5+) (chromium(III) meso-tetrakis(2,3,5,6-tetrafluoro-N,N,N-trimethyl-4-anilinium)yl) porphyrin) was synthesized and the spectral and electrochemical properties were examined. In aqueous solution, [Cr(111)TF(4)TMAp](5+) exhibits two pK(a)s at 7.04 and 10.07. The cyclic voltammogram showed that a reversible reduction wave appeared at -0.84 V in pH 5.0 buffer solution, which is assigned as the Cr-III/II redox couple. The oxidation formal potentials were obtained by spectroelectrochemistry. With suitable control of the oxidation potentials and solution conditions, the high valent oxo-Cr-1V and oxo-Cr-v porphyrins were obtained. The ligand trans to the oxygen atom is either H2O or OH-, depending on the pH of the solution. In this paper, oxo-(CrTF)-T-v (4)TMAP is thus the first reported water-soluble Cr-v porphyrin that can be generated electrochemically and chemically. Electrogenerated oxo-Cr-v porphyrin species catalyzed the oxidation of cyclopent-2-ene-1-acetic acid to cyclopent-2-ene-4-one-1-acetic acid in the presence of dioxygen and returned to oxo-Cr-1v porphyrin, which is not reactive toward the substrate. (C) 2003 Elsevier B.V. All rights reserved.