Identification of a Two-Coordinate Iron(I)–Oxalate Complex

Martin Mayer; Nina Vankova; Ferdinand Stolz; Bernd Abel; Thomas Heine; Knut R. Asmis

doi:10.1002/anie.202117855

Identification of a Two-Coordinate Iron(I)–Oxalate Complex

Martin Mayer, Nina Vankova, Ferdinand Stolz, Bernd Abel, Thomas Heine, Knut R. Asmis

Department of Chemistry

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

1 Citation (Scopus)

Abstract

Exotic oxidation states of the first-row transition metals have recently attracted much interest. In order to investigate the oxidation states of a series of iron–oxalate complexes, an aqueous solution of iron(III) nitrate and oxalic acid was studied by infrared free liquid matrix-assisted laser desorption/ionization as well as ionspray mass spectrometry. Here, we show that iron is not only detected in its common oxidation states +II and +III, but also in its unusual oxidation state +I, detectable in both positive-ion and in negative-ion modes, respectively. Vibrational spectra of the gas phase anionic iron oxalate complexes [Fe^III(C₂O₄)₂]⁻, [Fe^II(C₂O₄)CO₂]⁻, and [Fe^I(C₂O₄)]⁻ were measured by means of infrared photodissociation spectroscopy and their structures were assigned by comparison to anharmonic vibrational spectra based on second-order perturbation theory.

Original language	English
Article number	e202117855
Journal	Angewandte Chemie - International Edition
Volume	61
Issue number	16
DOIs	https://doi.org/10.1002/anie.202117855
Publication status	Published - 2022 Apr 11

Bibliographical note

Funding Information:
K.R.A. acknowledges instrumental support from the Fritz-Haber-Institute of the Max-Planck-Society. N.V. and T.H. thank ZIH Dresden for providing computational resources. B.A. and F.S. thank the German Science Foundation (DFG) for funding within the Research Unit FOR 2177. Open Access funding enabled and organized by Projekt DEAL.

Funding Information:
K.R.A. acknowledges instrumental support from the Fritz‐Haber‐Institute of the Max‐Planck‐Society. N.V. and T.H. thank ZIH Dresden for providing computational resources. B.A. and F.S. thank the German Science Foundation (DFG) for funding within the Research Unit FOR 2177. Open Access funding enabled and organized by Projekt DEAL.

Publisher Copyright:
© 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.

All Science Journal Classification (ASJC) codes

Catalysis
Chemistry(all)

Access to Document

10.1002/anie.202117855

Cite this

@article{fe9f3b0c0b0245089e1bc3df66683c55,

title = "Identification of a Two-Coordinate Iron(I)–Oxalate Complex",

abstract = "Exotic oxidation states of the first-row transition metals have recently attracted much interest. In order to investigate the oxidation states of a series of iron–oxalate complexes, an aqueous solution of iron(III) nitrate and oxalic acid was studied by infrared free liquid matrix-assisted laser desorption/ionization as well as ionspray mass spectrometry. Here, we show that iron is not only detected in its common oxidation states +II and +III, but also in its unusual oxidation state +I, detectable in both positive-ion and in negative-ion modes, respectively. Vibrational spectra of the gas phase anionic iron oxalate complexes [FeIII(C2O4)2]−, [FeII(C2O4)CO2]−, and [FeI(C2O4)]− were measured by means of infrared photodissociation spectroscopy and their structures were assigned by comparison to anharmonic vibrational spectra based on second-order perturbation theory.",

author = "Martin Mayer and Nina Vankova and Ferdinand Stolz and Bernd Abel and Thomas Heine and Asmis, {Knut R.}",

note = "Funding Information: K.R.A. acknowledges instrumental support from the Fritz-Haber-Institute of the Max-Planck-Society. N.V. and T.H. thank ZIH Dresden for providing computational resources. B.A. and F.S. thank the German Science Foundation (DFG) for funding within the Research Unit FOR 2177. Open Access funding enabled and organized by Projekt DEAL. Funding Information: K.R.A. acknowledges instrumental support from the Fritz‐Haber‐Institute of the Max‐Planck‐Society. N.V. and T.H. thank ZIH Dresden for providing computational resources. B.A. and F.S. thank the German Science Foundation (DFG) for funding within the Research Unit FOR 2177. Open Access funding enabled and organized by Projekt DEAL. Publisher Copyright: {\textcopyright} 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.",

year = "2022",

month = apr,

day = "11",

doi = "10.1002/anie.202117855",

language = "English",

volume = "61",

journal = "Angewandte Chemie - International Edition",

issn = "1433-7851",

publisher = "John Wiley and Sons Ltd",

number = "16",

}

TY - JOUR

T1 - Identification of a Two-Coordinate Iron(I)–Oxalate Complex

AU - Mayer, Martin

AU - Vankova, Nina

AU - Stolz, Ferdinand

AU - Abel, Bernd

AU - Heine, Thomas

AU - Asmis, Knut R.

N1 - Funding Information: K.R.A. acknowledges instrumental support from the Fritz-Haber-Institute of the Max-Planck-Society. N.V. and T.H. thank ZIH Dresden for providing computational resources. B.A. and F.S. thank the German Science Foundation (DFG) for funding within the Research Unit FOR 2177. Open Access funding enabled and organized by Projekt DEAL. Funding Information: K.R.A. acknowledges instrumental support from the Fritz‐Haber‐Institute of the Max‐Planck‐Society. N.V. and T.H. thank ZIH Dresden for providing computational resources. B.A. and F.S. thank the German Science Foundation (DFG) for funding within the Research Unit FOR 2177. Open Access funding enabled and organized by Projekt DEAL. Publisher Copyright: © 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.

PY - 2022/4/11

Y1 - 2022/4/11

N2 - Exotic oxidation states of the first-row transition metals have recently attracted much interest. In order to investigate the oxidation states of a series of iron–oxalate complexes, an aqueous solution of iron(III) nitrate and oxalic acid was studied by infrared free liquid matrix-assisted laser desorption/ionization as well as ionspray mass spectrometry. Here, we show that iron is not only detected in its common oxidation states +II and +III, but also in its unusual oxidation state +I, detectable in both positive-ion and in negative-ion modes, respectively. Vibrational spectra of the gas phase anionic iron oxalate complexes [FeIII(C2O4)2]−, [FeII(C2O4)CO2]−, and [FeI(C2O4)]− were measured by means of infrared photodissociation spectroscopy and their structures were assigned by comparison to anharmonic vibrational spectra based on second-order perturbation theory.

AB - Exotic oxidation states of the first-row transition metals have recently attracted much interest. In order to investigate the oxidation states of a series of iron–oxalate complexes, an aqueous solution of iron(III) nitrate and oxalic acid was studied by infrared free liquid matrix-assisted laser desorption/ionization as well as ionspray mass spectrometry. Here, we show that iron is not only detected in its common oxidation states +II and +III, but also in its unusual oxidation state +I, detectable in both positive-ion and in negative-ion modes, respectively. Vibrational spectra of the gas phase anionic iron oxalate complexes [FeIII(C2O4)2]−, [FeII(C2O4)CO2]−, and [FeI(C2O4)]− were measured by means of infrared photodissociation spectroscopy and their structures were assigned by comparison to anharmonic vibrational spectra based on second-order perturbation theory.

UR - http://www.scopus.com/inward/record.url?scp=85125166593&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85125166593&partnerID=8YFLogxK

U2 - 10.1002/anie.202117855

DO - 10.1002/anie.202117855

M3 - Article

C2 - 35088489

AN - SCOPUS:85125166593

SN - 1433-7851

VL - 61

JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

IS - 16

M1 - e202117855

ER -

Identification of a Two-Coordinate Iron(I)–Oxalate Complex

Abstract

Bibliographical note

All Science Journal Classification (ASJC) codes

Access to Document

Other files and links

Fingerprint

Cite this