Inorganic Chemistry, volume 62, issue 27, pages 10613-10625
Homoleptic Fe(III) and Fe(IV) Complexes of a Dianionic C3-Symmetric Scorpionate
Tretiakov Serhii
1
,
Lutz Martin
2
,
Titus Charles James
3
,
Nehrkorn Joscha
5
,
Lohmiller T
6
,
Holldack Karsten
7
,
Schnegg A.
5
,
Tarrago Maxime François Xavier
8
,
Zhang Peng
9, 10
,
Ye Shengfa
9
,
Aleshin Dmitry
11
,
PAVLOV ALEXANDER
11, 12
,
Novikov Valentin V
12
,
Moret Marc Etienne
1
1
Organic Chemistry & Catalysis, Institute for Sustainable and Circular Chemistry, Utrecht University, 3584 CG Utrecht, The Netherlands
|
2
Structural Biochemistry, Bijvoet Centre for Biomolecular Research, Faculty of Science, Utrecht University, 3584 CG Utrecht, The Netherlands
|
4
Materials Chemistry & Catalysis, Debye Institute for Materials Science, Utrecht University, 3584 CG Utrecht, The Netherlands
|
5
Max-Planck-Institute for Chemical Energy Conversion, EPR Research Group, 45470 Mülheim/Ruhr, Germany
|
6
Department Spins in Energy Conversion and Quantum Information Science, Helmholtz Zentrum Berlin für Materialien und Energie GmbH, EPR4 Energy Joint Lab, 12489 Berlin, Germany
|
7
Department of Optics and Beamlines, Helmholtz Zentrum Berlin für Materialien und Energie GmbH, 12489 Berlin, Germany
|
8
Department of Molecular Theory and Spectroscopy, Max Planck Institut für Kohlenforschung, 45470 Mülheim/Ruhr, Germany
|
9
State Key Laboratory of catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, P. R. China
|
Publication type: Journal Article
Publication date: 2023-06-27
Journal:
Inorganic Chemistry
Quartile SCImago
Q1
Quartile WOS
Q1
Impact factor: 4.6
ISSN: 00201669, 1520510X
Inorganic Chemistry
Physical and Theoretical Chemistry
Abstract
High-valent iron species have been implicated as key intermediates in catalytic oxidation reactions, both in biological and synthetic systems. Many heteroleptic Fe(IV) complexes have now been prepared and characterized, especially using strongly π-donating oxo, imido, or nitrido ligands. On the other hand, homoleptic examples are scarce. Herein, we investigate the redox chemistry of iron complexes of the dianonic tris-skatylmethylphosphonium (TSMP2–) scorpionate ligand. One-electron oxidation of the tetrahedral, bis-ligated [(TSMP)2FeII]2– leads to the octahedral [(TSMP)2FeIII]−. The latter undergoes thermal spin-cross-over both in the solid state and solution, which we characterize using superconducting quantum inference device (SQUID), Evans method, and paramagnetic nuclear magnetic resonance spectroscopy. Furthermore, [(TSMP)2FeIII]− can be reversibly oxidized to the stable high-valent [(TSMP)2FeIV]0 complex. We use a variety of electrochemical, spectroscopic, and computational techniques as well as SQUID magnetometry to establish a triplet (S = 1) ground state with a metal-centered oxidation and little spin delocalization on the ligand. The complex also has a fairly isotropic g-tensor (giso = 1.97) combined with a positive zero-field splitting (ZFS) parameter D (+19.1 cm–1) and very low rhombicity, in agreement with quantum chemical calculations. This thorough spectroscopic characterization contributes to a general understanding of octahedral Fe(IV) complexes.
Citations by journals
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1
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Angewandte Chemie - International Edition
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Angewandte Chemie - International Edition
1 publication, 50%
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Angewandte Chemie
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Angewandte Chemie
1 publication, 50%
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1
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Citations by publishers
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1
2
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Wiley
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Wiley
2 publications, 100%
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1
2
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Tretiakov S. et al. Homoleptic Fe(III) and Fe(IV) Complexes of a Dianionic C3-Symmetric Scorpionate // Inorganic Chemistry. 2023. Vol. 62. No. 27. pp. 10613-10625.
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Tretiakov S., Lutz M., Titus C. J., de Groot F. M. F., Nehrkorn J., Lohmiller T., Holldack K., Schnegg A., Tarrago M. F. X., Zhang P., Ye S., Aleshin D., PAVLOV A., Novikov V. V., Moret M. E. Homoleptic Fe(III) and Fe(IV) Complexes of a Dianionic C3-Symmetric Scorpionate // Inorganic Chemistry. 2023. Vol. 62. No. 27. pp. 10613-10625.
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TY - JOUR
DO - 10.1021/acs.inorgchem.3c00871
UR - https://doi.org/10.1021%2Facs.inorgchem.3c00871
TI - Homoleptic Fe(III) and Fe(IV) Complexes of a Dianionic C3-Symmetric Scorpionate
T2 - Inorganic Chemistry
AU - Tretiakov, Serhii
AU - Lutz, Martin
AU - Titus, Charles James
AU - de Groot, F. M. F.
AU - Nehrkorn, Joscha
AU - Lohmiller, T
AU - Holldack, Karsten
AU - Schnegg, A.
AU - Tarrago, Maxime François Xavier
AU - Zhang, Peng
AU - Ye, Shengfa
AU - Aleshin, Dmitry
AU - PAVLOV, ALEXANDER
AU - Novikov, Valentin V
AU - Moret, Marc Etienne
PY - 2023
DA - 2023/06/27 00:00:00
PB - American Chemical Society (ACS)
SP - 10613-10625
IS - 27
VL - 62
SN - 0020-1669
SN - 1520-510X
ER -
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@article{2023_Tretiakov,
author = {Serhii Tretiakov and Martin Lutz and Charles James Titus and F. M. F. de Groot and Joscha Nehrkorn and T Lohmiller and Karsten Holldack and A. Schnegg and Maxime François Xavier Tarrago and Peng Zhang and Shengfa Ye and Dmitry Aleshin and ALEXANDER PAVLOV and Valentin V Novikov and Marc Etienne Moret},
title = {Homoleptic Fe(III) and Fe(IV) Complexes of a Dianionic C3-Symmetric Scorpionate},
journal = {Inorganic Chemistry},
year = {2023},
volume = {62},
publisher = {American Chemical Society (ACS)},
month = {jun},
url = {https://doi.org/10.1021%2Facs.inorgchem.3c00871},
number = {27},
pages = {10613--10625},
doi = {10.1021/acs.inorgchem.3c00871}
}
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Tretiakov, Serhii, et al. “Homoleptic Fe(III) and Fe(IV) Complexes of a Dianionic C3-Symmetric Scorpionate.” Inorganic Chemistry, vol. 62, no. 27, Jun. 2023, pp. 10613-10625. https://doi.org/10.1021%2Facs.inorgchem.3c00871.