Synthesis and structure of [Fe13O4F24(OME)12]5-: The first open-shell Keggin ion

Avi Bino; Michael Ardon; Dongwhan Lee; Bernhard Spingler; Stephen J. Lippard

doi:10.1021/ja025590a

Synthesis and structure of [Fe₁₃O₄F₂₄(OME)₁₂]^5-: The first open-shell Keggin ion

Avi Bino
, Michael Ardon
, Dongwhan Lee
, Bernhard Spingler
, Stephen J. Lippard^*

^*Corresponding author for this work

Institute of Chemistry

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

84 Scopus citations

Abstract

The reaction between ferric fluoride trihydrate and pyridine in hot methanol produced yellow-brown crystals of (PyH)₅·[Fe₁₃O₄F₂₄(OMe)₁₂]·4H₂O·CH₃OH. The anionic complex [Fe₁₃O₄F₂₄(OMe)₁₂]^5- (1), which has a full T_d symmetry, is the first example of an open-shell Keggin ion consisting of 13 high-spin d5 iron(III) atoms. The central, tetrahedral {FeO₄} unit in 1 is surrounded by 12 octahedral iron atoms, which are bridged by methoxide oxygen atoms and fluoride ligands. In addition, each of the 12 iron atoms is coordinated to a terminal fluoride ligand with an Fe-F distance of 1.846(3) Å. Magnetic susceptibility studies indicate strong exchange interactions between the iron atoms, the μ_eff value of 19.3 μ_B at 300 K being significantly lower than that expected for thirteen uncoupled S = 5/2 centers.

Original language	English
Pages (from-to)	4578-4579
Number of pages	2
Journal	Journal of the American Chemical Society
Volume	124
Issue number	17
DOIs	https://doi.org/10.1021/ja025590a
State	Published - 1 May 2002

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@article{efe5eb2c4f614335800e17b50ff1f289,

title = "Synthesis and structure of [Fe13O4F24(OME)12]5-: The first open-shell Keggin ion",

abstract = "The reaction between ferric fluoride trihydrate and pyridine in hot methanol produced yellow-brown crystals of (PyH)5·[Fe13O4F24(OMe)12]·4H2O·CH3OH. The anionic complex [Fe13O4F24(OMe)12]5- (1), which has a full Td symmetry, is the first example of an open-shell Keggin ion consisting of 13 high-spin d5 iron(III) atoms. The central, tetrahedral \{FeO4\} unit in 1 is surrounded by 12 octahedral iron atoms, which are bridged by methoxide oxygen atoms and fluoride ligands. In addition, each of the 12 iron atoms is coordinated to a terminal fluoride ligand with an Fe-F distance of 1.846(3) {\AA}. Magnetic susceptibility studies indicate strong exchange interactions between the iron atoms, the μeff value of 19.3 μB at 300 K being significantly lower than that expected for thirteen uncoupled S = 5/2 centers.",

author = "Avi Bino and Michael Ardon and Dongwhan Lee and Bernhard Spingler and Lippard, \{Stephen J.\}",

year = "2002",

month = may,

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doi = "10.1021/ja025590a",

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T1 - Synthesis and structure of [Fe13O4F24(OME)12]5-

T2 - The first open-shell Keggin ion

AU - Bino, Avi

AU - Ardon, Michael

AU - Lee, Dongwhan

AU - Spingler, Bernhard

AU - Lippard, Stephen J.

PY - 2002/5/1

Y1 - 2002/5/1

N2 - The reaction between ferric fluoride trihydrate and pyridine in hot methanol produced yellow-brown crystals of (PyH)5·[Fe13O4F24(OMe)12]·4H2O·CH3OH. The anionic complex [Fe13O4F24(OMe)12]5- (1), which has a full Td symmetry, is the first example of an open-shell Keggin ion consisting of 13 high-spin d5 iron(III) atoms. The central, tetrahedral {FeO4} unit in 1 is surrounded by 12 octahedral iron atoms, which are bridged by methoxide oxygen atoms and fluoride ligands. In addition, each of the 12 iron atoms is coordinated to a terminal fluoride ligand with an Fe-F distance of 1.846(3) Å. Magnetic susceptibility studies indicate strong exchange interactions between the iron atoms, the μeff value of 19.3 μB at 300 K being significantly lower than that expected for thirteen uncoupled S = 5/2 centers.

AB - The reaction between ferric fluoride trihydrate and pyridine in hot methanol produced yellow-brown crystals of (PyH)5·[Fe13O4F24(OMe)12]·4H2O·CH3OH. The anionic complex [Fe13O4F24(OMe)12]5- (1), which has a full Td symmetry, is the first example of an open-shell Keggin ion consisting of 13 high-spin d5 iron(III) atoms. The central, tetrahedral {FeO4} unit in 1 is surrounded by 12 octahedral iron atoms, which are bridged by methoxide oxygen atoms and fluoride ligands. In addition, each of the 12 iron atoms is coordinated to a terminal fluoride ligand with an Fe-F distance of 1.846(3) Å. Magnetic susceptibility studies indicate strong exchange interactions between the iron atoms, the μeff value of 19.3 μB at 300 K being significantly lower than that expected for thirteen uncoupled S = 5/2 centers.

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Synthesis and structure of [Fe₁₃O₄F₂₄(OME)₁₂]^5-: The first open-shell Keggin ion

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