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Crystallographic Evidence for a Sterically Induced Ferryl Tilt in a Non-Heme Oxoiron(IV) Complex that Makes it a Better Oxidant
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DOI：10.1002/anie.201804836.png)
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Abstract
En 中文
Oxoiron(IV) units are often implicated as intermediates in the catalytic cycles of non-heme iron oxygenases and oxidases. The most reactive synthetic analogues of these intermediates are supported by tetradentate tripodal ligands with N-methylbenzimidazole or quinoline donors, but their instability precludes structural characterization. Herein we report crystal structures of two [Fe-IV(O)(L)](2+) complexes supported by pentadentate ligands incorporating these heterocycles, which show longer average Fe-N distances than the complex with only pyridine donors. These longer distances correlate linearly with logk(2) values for O- and H-atom transfer rates, suggesting that weakening the ligand field increases the electrophilicity of the Fe=O center. The sterically bulkier quinoline donors are also found to tilt the Fe=O unit away from a linear N-Fe=O arrangement by 10 degrees.
Keywords:
hydrogen atom transfer (HAT)
non-heme iron complexes
oxoiron(IV) complexes
two-state reactivity
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