Crystallographic Evidence for a Sterically Induced Ferryl Tilt in a Non-Heme Oxoiron(IV) Complex that Makes it a Better Oxidant

Waqas Rasheed; Apparao Draksharapu; Saikat Banerjee; Victor G Young; Ruixi Fan; Yisong Guo; M. Ozerov; Joscha Nehrkorn; J. Krzystek; Joshua Telser; Larry Que

doi:10.1002/anie.201804836

Crystallographic Evidence for a Sterically Induced Ferryl Tilt in a Non-Heme Oxoiron(IV) Complex that Makes it a Better Oxidant

Waqas Rasheed, Apparao Draksharapu, Saikat Banerjee, Victor G Young, Ruixi Fan, Yisong Guo, M. Ozerov, Joscha Nehrkorn, J. Krzystek, Joshua Telser, Larry Que

Chemistry (Twin Cities)

Research output: Contribution to journal › Article › peer-review

24 Scopus citations

Abstract

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 log k₂′ 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°.

Original language	English (US)
Pages (from-to)	9387-9391
Number of pages	5
Journal	Angewandte Chemie - International Edition
Volume	57
Issue number	30
DOIs	https://doi.org/10.1002/anie.201804836
State	Published - Jul 20 2018

Bibliographical note

Funding Information:
This work was supported by grants from the U.S. National Science Foundation (CHE-1665391 to L.Q. and CHE-1654060 to Y.G.). The National High Magnetic Field Laboratory is supported by U.S. National Science Foundation through Cooperative Agreement DMR-1644779 and the State of Florida. The Bruker-AXS D8 Venture Diffractometer was purchased through a grant from NSF/MRI 1229400 and the University of Minnesota. We thank Prof. Steven Kass for the use of their FTIR spectrometer and the reviewers for their helpful suggestions.

Keywords

hydrogen atom transfer (HAT)
non-heme iron complexes
oxoiron(IV) complexes
two-state reactivity

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Rasheed, W., Draksharapu, A., Banerjee, S., Young, V. G., Fan, R., Guo, Y., Ozerov, M., Nehrkorn, J., Krzystek, J., Telser, J., & Que, L. (2018). Crystallographic Evidence for a Sterically Induced Ferryl Tilt in a Non-Heme Oxoiron(IV) Complex that Makes it a Better Oxidant. Angewandte Chemie - International Edition, 57(30), 9387-9391. https://doi.org/10.1002/anie.201804836

Crystallographic Evidence for a Sterically Induced Ferryl Tilt in a Non-Heme Oxoiron(IV) Complex that Makes it a Better Oxidant. / Rasheed, Waqas; Draksharapu, Apparao; Banerjee, Saikat; Young, Victor G; Fan, Ruixi; Guo, Yisong; Ozerov, M.; Nehrkorn, Joscha; Krzystek, J.; Telser, Joshua; Que, Larry.

In: Angewandte Chemie - International Edition, Vol. 57, No. 30, 20.07.2018, p. 9387-9391.

Research output: Contribution to journal › Article › peer-review

Rasheed, W, Draksharapu, A, Banerjee, S, Young, VG, Fan, R, Guo, Y, Ozerov, M, Nehrkorn, J, Krzystek, J, Telser, J & Que, L 2018, 'Crystallographic Evidence for a Sterically Induced Ferryl Tilt in a Non-Heme Oxoiron(IV) Complex that Makes it a Better Oxidant', Angewandte Chemie - International Edition, vol. 57, no. 30, pp. 9387-9391. https://doi.org/10.1002/anie.201804836

Rasheed, Waqas ; Draksharapu, Apparao ; Banerjee, Saikat ; Young, Victor G ; Fan, Ruixi ; Guo, Yisong ; Ozerov, M. ; Nehrkorn, Joscha ; Krzystek, J. ; Telser, Joshua ; Que, Larry. / Crystallographic Evidence for a Sterically Induced Ferryl Tilt in a Non-Heme Oxoiron(IV) Complex that Makes it a Better Oxidant. In: Angewandte Chemie - International Edition. 2018 ; Vol. 57, No. 30. pp. 9387-9391.

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abstract = "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 [FeIV(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 log k2′ 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°.",

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