Electron-Transfer Kinetics for Generation of Organoiron(IV) Porphyrins and the Iron(IV) Porphyrin π Radical Cations

1999

Homogeneous electron-transfer kinetics for the oxidation of seven different iron(III) porphyrins using three different oxidants were examined in deaerated acetonitrile, and the resulting data were evaluated in light of the Marcus theory of electron transfer to determine reorganization energies of the rate-determining oxidation of iron(III) to iron(IV). The investigated compounds are represented as (P)Fe(R), where P = the dianion of 2,3,7,8,12,13,17,18-octaethyl-5,10,15,20-tetraphenylporphyrin (OETPP) and R = C6H5, 3,5-C6F2H3, 2,4,6-C6F3H2, or C6F5 or P = the dianion of 2,3,7,8,12,13,17,18-octaethylporphyrin (OEP) and R = C6H5, 2,4,6-C6F3H2, or 2,3,5,6-C6F4H. The first one-electron transfer …