Xα multiple scattering calculations are reported for the d4 oxo complexes Fe(P)(py)(O)0, 1+(P = porphine, py = pyridine), models for the active sites of intermediates I and II of horseradish peroxidase. Orbital energy trends for the addition of pyridine and then oxygen to Fe(II) porphine are used to rationalize spin and oxidation states of these clusters. Particular attention is paid to comparisons with ENDOR spectral data on intermediate I. Our results suggest that both a and ir spin transfer to the ligands is important and that the spins localized at the FeO and porphyrin sites interact strongly.
All Science Journal Classification (ASJC) codes
- Colloid and Surface Chemistry