Experimental electronic structures of the Fe ^IV =O bond in S=1 heme vs. nonheme sites: Effect of the porphyrin ligand

Proceedings of the National Academy of Sciences, Journal Year: 2025, Volume and Issue: 122(8)

Published: Feb. 21, 2025

High-valent Fe IV =O species are common intermediates in biological and artificial catalysts. Heme nonheme S=1 sites have been synthesized studied for decades but little quantitative experimental comparison of their electronic structures has available, due to the lack direct methods focused on iron. This study allows a rigorous determination structure center its an heme site using 1s2p resonant inelastic X-ray scattering (RIXS) L-edge absorption spectroscopy (XAS). Further, variable temperature magnetic circular dichroism (VT-MCD) ligand field transitions, combined with nuclear resonance vibrational two systems show that equatorial decreases from site. Alternatively, RIXS XAS MCD d π orbitals unperturbed relative because strong axial Fe-O bond uncouples porphyrin -system. As consequence, thermodynamics kinetics H-atom abstraction reactions actually very similar compound II active sites.

Language: Английский

Bioinorganic Chemistry: A Field Where Biomimetism and Bioinspiration Are Central

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(50), P. 23475 - 23478

Published: Dec. 16, 2024

Language: Английский