10.1021/jp030817p.s001
Jeanet Conradie
Jeanet
Conradie
Jannie C. Swarts
Jannie C.
Swarts
Abhik Ghosh
Abhik
Ghosh
Models of High-Valent Heme Protein Intermediates: A Quantum Chemical Study of
Iron(IV) Porphyrins with Two Univalent Axial π-Bonding Ligands
American Chemical Society
2004
Quantum Chemical Study
quantum chemical survey
intermediate
chemical reactivity
oxo ligand
cytochromes P 450
heme proteins
metal center
2004-01-08 00:00:00
Journal contribution
https://acs.figshare.com/articles/journal_contribution/Models_of_High_Valent_Heme_Protein_Intermediates_A_Quantum_Chemical_Study_of_Iron_IV_Porphyrins_with_Two_Univalent_Axial_Bonding_Ligands/3353989
This is a quantum chemical survey of a broad class of high-valent transition metal intermediates relevant to
the catalytic cycles of the cytochromes P<sub>450</sub> and related heme proteins, viz. iron(IV) and manganese(IV)
porphyrins with two univalent π-bonding axial ligands. The axial ligands in these intermediates invariably
exhibit a bent geometry, reflecting a competitive interplay of σ- and π-bonding effects. Compared to an oxo
ligand, the univalent ligands are distinctly less able to delocalize electronic spin density away from the metal
center, which might have significant implications for the chemical reactivity of these species.