Abstract
Compound I and compound II of heme peroxidases represent high-valent iron complexes with iron in the formal oxidation state IV. Reliable information about their magnetic and electronic properties requires the applications of complementary techniques like Mössbauer and EPR spectroscopy, magnetic susceptibility measurements and theoretical calculations. In order to study the physical properties of the high-valent iron moiety, a series of novel porphyrin-like complexes has been investigated, obtained with the planar N4-donating ligand L=pentane-2,4-dion-bis(S-alkylisothiosemicarbazonate). Due to their symmetry and their ability of binding a variety of axial ligands of biological relevance, these complexes can serve as biomimetic models for high-valent iron-porphyrin complexes. 5-coordinated and 6-coordinated complexes differ significantly in their spin states (5=1 versusS=0), whereas Mössbauer and XAS spectra are similar. MO calculations based on experimental molecular structures provide deeper understanding of theelectronic structure of these compounds. They reveal the formal nature of the concept of oxidation number in descriptions of high-valent complexes, in the sense that these numbers cannot be correlated with empirical data.
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Bill, E. High oxidation states of iron in biological and biomimetical systems: Complementary Mössbauer, EPR and magnetic susceptibility studies. Hyperfine Interact 90, 143–158 (1994). https://doi.org/10.1007/BF02069124
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DOI: https://doi.org/10.1007/BF02069124