Oxoferryl porphyrin pi -cation radical active sites of compound I intermedi
ates which, are found in enzymes such as peroxidases and catalases have bee
n extensively modeled by oxidized synthetic metalloporphyrins. The electron
ic symmetry states of these compounds were initially assigned on the basis
of electronic absorption data. in recent years new experimental and theoret
ical results have become available which have led to a re-evaluation and mo
dification of the original assignments. A historical perspective of these d
evelopments is provided in the context of recent NMR, resonance Raman, and
other spectroscopic data and theoretical calculations for the synthetic mod
els and enzymatic systems. Copyright (C) 2001 John Wiley & Sons, Ltd.