Structural insights into nonheme alkylperoxoiron(III) and oxoiron(IV) intermediates by X-ray absorption spectroscopy

Jan Uwe Ronde; Stéphane Torelli; Xiaopeng Shan; Hee Lim Mi; Eric J. Klinker; József Kaizer; Kui Chen; Wonwoo Nam; Lawrence Que

doi:10.1021/ja047667w

Structural insights into nonheme alkylperoxoiron(III) and oxoiron(IV) intermediates by X-ray absorption spectroscopy

Jan Uwe Ronde, Stéphane Torelli, Xiaopeng Shan, Hee Lim Mi, Eric J. Klinker, József Kaizer, Kui Chen, Wonwoo Nam, Lawrence Que

Chemistry (Twin Cities)

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

141 Scopus citations

Abstract

Transient mononuclear low-spin alkylperoxoiron(III) and oxoiron(IV) complexes that are relevant to the activation of dioxygen by nonheme iron enzymes have been generated from synthetic iron(II) complexes of neutral tetradentate (TPA) and pentadentate (N4Py, Bn-TPEN) ligands and structurally characterized by means of Fe K-edge X-ray absorption spectroscopy (XAS). Notable features obtained from fits of the EXAFS region are Fe-O bond lengths of 1.78 Å for the alkylperoxoiron(III) intermediates and 1.65-1.68 Å for the oxoiron(IV) intermediates, reflecting different strengths in the Fe-O π interactions. These differences are also observed in the intensities of the 1s-to-3d transitions in the XANES region, which increase from 4 units for the nearly octahedral iron(II) precursor to 9-15 units for the alkylperoxoiron(III) intermediates to 25-29 units for the oxoiron(IV) species.

Original language	English (US)
Pages (from-to)	16750-16761
Number of pages	12
Journal	Journal of the American Chemical Society
Volume	126
Issue number	51
DOIs	https://doi.org/10.1021/ja047667w
State	Published - Dec 29 2004

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title = "Structural insights into nonheme alkylperoxoiron(III) and oxoiron(IV) intermediates by X-ray absorption spectroscopy",

abstract = "Transient mononuclear low-spin alkylperoxoiron(III) and oxoiron(IV) complexes that are relevant to the activation of dioxygen by nonheme iron enzymes have been generated from synthetic iron(II) complexes of neutral tetradentate (TPA) and pentadentate (N4Py, Bn-TPEN) ligands and structurally characterized by means of Fe K-edge X-ray absorption spectroscopy (XAS). Notable features obtained from fits of the EXAFS region are Fe-O bond lengths of 1.78 {\AA} for the alkylperoxoiron(III) intermediates and 1.65-1.68 {\AA} for the oxoiron(IV) intermediates, reflecting different strengths in the Fe-O π interactions. These differences are also observed in the intensities of the 1s-to-3d transitions in the XANES region, which increase from 4 units for the nearly octahedral iron(II) precursor to 9-15 units for the alkylperoxoiron(III) intermediates to 25-29 units for the oxoiron(IV) species.",

author = "Ronde, {Jan Uwe} and St{\'e}phane Torelli and Xiaopeng Shan and Mi, {Hee Lim} and Klinker, {Eric J.} and J{\'o}zsef Kaizer and Kui Chen and Wonwoo Nam and Lawrence Que",

year = "2004",

month = dec,

day = "29",

doi = "10.1021/ja047667w",

language = "English (US)",

volume = "126",

pages = "16750--16761",

journal = "Journal of the American Chemical Society",

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publisher = "American Chemical Society",

number = "51",

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TY - JOUR

T1 - Structural insights into nonheme alkylperoxoiron(III) and oxoiron(IV) intermediates by X-ray absorption spectroscopy

AU - Ronde, Jan Uwe

AU - Torelli, Stéphane

AU - Shan, Xiaopeng

AU - Mi, Hee Lim

AU - Klinker, Eric J.

AU - Kaizer, József

AU - Chen, Kui

AU - Nam, Wonwoo

AU - Que, Lawrence

PY - 2004/12/29

Y1 - 2004/12/29

N2 - Transient mononuclear low-spin alkylperoxoiron(III) and oxoiron(IV) complexes that are relevant to the activation of dioxygen by nonheme iron enzymes have been generated from synthetic iron(II) complexes of neutral tetradentate (TPA) and pentadentate (N4Py, Bn-TPEN) ligands and structurally characterized by means of Fe K-edge X-ray absorption spectroscopy (XAS). Notable features obtained from fits of the EXAFS region are Fe-O bond lengths of 1.78 Å for the alkylperoxoiron(III) intermediates and 1.65-1.68 Å for the oxoiron(IV) intermediates, reflecting different strengths in the Fe-O π interactions. These differences are also observed in the intensities of the 1s-to-3d transitions in the XANES region, which increase from 4 units for the nearly octahedral iron(II) precursor to 9-15 units for the alkylperoxoiron(III) intermediates to 25-29 units for the oxoiron(IV) species.

AB - Transient mononuclear low-spin alkylperoxoiron(III) and oxoiron(IV) complexes that are relevant to the activation of dioxygen by nonheme iron enzymes have been generated from synthetic iron(II) complexes of neutral tetradentate (TPA) and pentadentate (N4Py, Bn-TPEN) ligands and structurally characterized by means of Fe K-edge X-ray absorption spectroscopy (XAS). Notable features obtained from fits of the EXAFS region are Fe-O bond lengths of 1.78 Å for the alkylperoxoiron(III) intermediates and 1.65-1.68 Å for the oxoiron(IV) intermediates, reflecting different strengths in the Fe-O π interactions. These differences are also observed in the intensities of the 1s-to-3d transitions in the XANES region, which increase from 4 units for the nearly octahedral iron(II) precursor to 9-15 units for the alkylperoxoiron(III) intermediates to 25-29 units for the oxoiron(IV) species.

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JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 51

ER -

Structural insights into nonheme alkylperoxoiron(III) and oxoiron(IV) intermediates by X-ray absorption spectroscopy

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