Structural and spectroscopic characterization of an Fe(VI) bis(imido) complex

Jorge L. Martinez; Sean A. Lutz; Hao Yang; Jiaze Xie; Joshua Telser; Brian M. Hoffman; Veronica Carta; Maren Pink; Yaroslav Losovyj; Jeremy M. Smith

doi:10.1126/science.abd3054

Structural and spectroscopic characterization of an Fe(VI) bis(imido) complex

Jorge L. Martinez, Sean A. Lutz, Hao Yang, Jiaze Xie, Joshua Telser, Brian M. Hoffman, Veronica Carta, Maren Pink, Yaroslav Losovyj, Jeremy M. Smith^*

^*Corresponding author for this work

Chemistry

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

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Abstract

High-valent iron species are key intermediates in oxidative biological processes, but hexavalent complexes apart from the ferrate ion are exceedingly rare. Here, we report the synthesis and structural and spectroscopic characterization of a stable Fe(VI) complex (3) prepared by facile one-electron oxidation of an Fe(V) bis(imido) (2). Single-crystal x-ray diffraction of 2 and 3 revealed four-coordinate Fe centers with an unusual “seesaw” geometry. ⁵⁷Fe Mössbauer, x-ray photoelectron, x-ray absorption, and electron-nuclear double resonance (ENDOR) spectroscopies, supported by electronic structure calculations, support a low-spin (S = 1/2) d³ Fe(V) configuration in 2 and a diamagnetic (S = 0) d² Fe(VI) configuration in 3. Their shared seesaw geometry is electronically dictated by a balance of Fe-imido s- and p-bonding interactions.

Original language	English (US)
Pages (from-to)	356-359
Number of pages	4
Journal	Science
Volume	370
Issue number	6514
DOIs	https://doi.org/10.1126/science.abd3054
State	Published - Oct 16 2020

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10.1126/science.abd3054

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@article{c2a697dedb394fd6a64f5609f3205786,

title = "Structural and spectroscopic characterization of an Fe(VI) bis(imido) complex",

abstract = "High-valent iron species are key intermediates in oxidative biological processes, but hexavalent complexes apart from the ferrate ion are exceedingly rare. Here, we report the synthesis and structural and spectroscopic characterization of a stable Fe(VI) complex (3) prepared by facile one-electron oxidation of an Fe(V) bis(imido) (2). Single-crystal x-ray diffraction of 2 and 3 revealed four-coordinate Fe centers with an unusual “seesaw” geometry. 57Fe M{\"o}ssbauer, x-ray photoelectron, x-ray absorption, and electron-nuclear double resonance (ENDOR) spectroscopies, supported by electronic structure calculations, support a low-spin (S = 1/2) d3 Fe(V) configuration in 2 and a diamagnetic (S = 0) d2 Fe(VI) configuration in 3. Their shared seesaw geometry is electronically dictated by a balance of Fe-imido s- and p-bonding interactions.",

author = "Martinez, {Jorge L.} and Lutz, {Sean A.} and Hao Yang and Jiaze Xie and Joshua Telser and Hoffman, {Brian M.} and Veronica Carta and Maren Pink and Yaroslav Losovyj and Smith, {Jeremy M.}",

note = "Funding Information: Funding from the NSF is gratefully acknowledged by J.L.M., S.A.L., and J.M.S. (CHE-1566258) and B.M.H. (MCB-1515981). This material is based upon work supported by the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences under award nos. DE-SC0019466 (to J.M.S.) and DE-SC0019342 (to B.M.H.). The XPS instrument at the IU Nanoscale Characterization Facility was funded by the NSF (DMR MRI-1126394). Support for the acquisition of the Bruker Venture D8 diffractometer through the Major Scientific Research Equipment Fund from the President of Indiana University and the Office of the Vice President for Research is gratefully acknowledged. NSF's ChemMatCARS Sector 15 is supported by the NSF Divisions of Chemistry (CHE) and Materials Research (DMR) under grant no. CHE-1834750. Use of the Advanced Photon Source, an Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory, was supported by DOE under contract no. DE-AC02-06CH11357. Publisher Copyright: {\textcopyright} 2020 American Association for the Advancement of Science. All rights reserved.",

year = "2020",

month = oct,

day = "16",

doi = "10.1126/science.abd3054",

language = "English (US)",

volume = "370",

pages = "356--359",

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T1 - Structural and spectroscopic characterization of an Fe(VI) bis(imido) complex

AU - Martinez, Jorge L.

AU - Lutz, Sean A.

AU - Yang, Hao

AU - Xie, Jiaze

AU - Telser, Joshua

AU - Hoffman, Brian M.

AU - Carta, Veronica

AU - Pink, Maren

AU - Losovyj, Yaroslav

AU - Smith, Jeremy M.

N1 - Funding Information: Funding from the NSF is gratefully acknowledged by J.L.M., S.A.L., and J.M.S. (CHE-1566258) and B.M.H. (MCB-1515981). This material is based upon work supported by the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences under award nos. DE-SC0019466 (to J.M.S.) and DE-SC0019342 (to B.M.H.). The XPS instrument at the IU Nanoscale Characterization Facility was funded by the NSF (DMR MRI-1126394). Support for the acquisition of the Bruker Venture D8 diffractometer through the Major Scientific Research Equipment Fund from the President of Indiana University and the Office of the Vice President for Research is gratefully acknowledged. NSF's ChemMatCARS Sector 15 is supported by the NSF Divisions of Chemistry (CHE) and Materials Research (DMR) under grant no. CHE-1834750. Use of the Advanced Photon Source, an Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory, was supported by DOE under contract no. DE-AC02-06CH11357. Publisher Copyright: © 2020 American Association for the Advancement of Science. All rights reserved.

PY - 2020/10/16

Y1 - 2020/10/16

N2 - High-valent iron species are key intermediates in oxidative biological processes, but hexavalent complexes apart from the ferrate ion are exceedingly rare. Here, we report the synthesis and structural and spectroscopic characterization of a stable Fe(VI) complex (3) prepared by facile one-electron oxidation of an Fe(V) bis(imido) (2). Single-crystal x-ray diffraction of 2 and 3 revealed four-coordinate Fe centers with an unusual “seesaw” geometry. 57Fe Mössbauer, x-ray photoelectron, x-ray absorption, and electron-nuclear double resonance (ENDOR) spectroscopies, supported by electronic structure calculations, support a low-spin (S = 1/2) d3 Fe(V) configuration in 2 and a diamagnetic (S = 0) d2 Fe(VI) configuration in 3. Their shared seesaw geometry is electronically dictated by a balance of Fe-imido s- and p-bonding interactions.

AB - High-valent iron species are key intermediates in oxidative biological processes, but hexavalent complexes apart from the ferrate ion are exceedingly rare. Here, we report the synthesis and structural and spectroscopic characterization of a stable Fe(VI) complex (3) prepared by facile one-electron oxidation of an Fe(V) bis(imido) (2). Single-crystal x-ray diffraction of 2 and 3 revealed four-coordinate Fe centers with an unusual “seesaw” geometry. 57Fe Mössbauer, x-ray photoelectron, x-ray absorption, and electron-nuclear double resonance (ENDOR) spectroscopies, supported by electronic structure calculations, support a low-spin (S = 1/2) d3 Fe(V) configuration in 2 and a diamagnetic (S = 0) d2 Fe(VI) configuration in 3. Their shared seesaw geometry is electronically dictated by a balance of Fe-imido s- and p-bonding interactions.

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DO - 10.1126/science.abd3054

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AN - SCOPUS:85093479152

SN - 0036-8075

VL - 370

SP - 356

EP - 359

JO - Science

JF - Science

IS - 6514

ER -

Structural and spectroscopic characterization of an Fe(VI) bis(imido) complex

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CCDC 1990356: Experimental Crystal Structure Determination

CCDC 1990357: Experimental Crystal Structure Determination

CCDC 1990355: Experimental Crystal Structure Determination

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Structural and spectroscopic characterization of an Fe(VI) bis(imido) complex

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CCDC 1990356: Experimental Crystal Structure Determination

CCDC 1990357: Experimental Crystal Structure Determination

CCDC 1990355: Experimental Crystal Structure Determination

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