Exploring the Frontiers of Heterometallic Systems: the {FeW<sub>5</sub>} Octahedral Cluster Complex

This research presents the first examples of heterometallic octahedral cluster complexes incorporating both 5d and 3d metals, specifically, tungsten and iron. The key compound, (TBA)<sub>2</sub>[FeW<sub>5</sub>Br<sub>14</sub>] (TBA = tetrabutylammonium), exhibits selective ligand substitution reactions at the iron site when exposed to various solvents. Several {FeW<sub>5</sub>}-type anions, namely, [FeW<sub>5</sub>Br<sub>14</sub>]<sup>2-</sup>, [FeW<sub>5</sub>Br<sub>13</sub>(L)]<sup>-</sup> (L = H<sub>2</sub>O, DMSO, CH<sub>3</sub>CN), and [(FeW<sub>5</sub>Br<sub>13</sub>)<sub>2</sub>O]<sup>4-</sup>, were revealed and characterized by single-crystal X-ray diffraction analysis. The redox properties of [FeW<sub>5</sub>Br<sub>14</sub>]<sup>2-</sup> were studied and compared with those of [W<sub>6</sub>Br<sub>14</sub>]<sup>2-</sup>. Density functional theory calculations demonstrated that the bonding between Fe and W atoms is fundamentally different from the bonding between 4d (Mo-Mo) or 5d (W-W) metals in isotypic {M<sub>6</sub>} clusters.

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Publication Details

Journal
Inorganic Chemistry
Published
2024-08-22
DOI
https://doi.org/10.1021/acs.inorgchem.4c02594
Citations
1
Primary Topic
Inorganic Chemistry and Materials
Type
article
Field-Weighted Citation Impact
0.16

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article

Exploring the Frontiers of Heterometallic Systems: the {FeW5} Octahedral Cluster Complex

Anton A. Ivanov, Vadim V. Yanshole, Darya V. Evtushok, Igor Asanov et al.
1 citations
Inorganic Chemistry
Inorganic Chemistry and Materials
0.16
article

Exploring the Frontiers of Heterometallic Systems: the {FeW5} Octahedral Cluster Complex

Anton A. Ivanov, Vadim V. Yanshole, Darya V. Evtushok, Igor Asanov, Vasiliy N. Yudin, Vasilii Yu. Evtushok, Michael A. Shestopalov, Yakov M. Gaifulin, Anastasia I. Kozyreva
article en
1 citations

Abstract

This research presents the first examples of heterometallic octahedral cluster complexes incorporating both 5d and 3d metals, specifically, tungsten and iron. The key compound, (TBA)<sub>2</sub>[FeW<sub>5</sub>Br<sub>14</sub>] (TBA = tetrabutylammonium), exhibits selective ligand substitution reactions at the iron site when exposed to various solvents. Several {FeW<sub>5</sub>}-type anions, namely, [FeW<sub>5</sub>Br<sub>14</sub>]<sup>2-</sup>, [FeW<sub>5</sub>Br<sub>13</sub>(L)]<sup>-</sup> (L = H<sub>2</sub>O, DMSO, CH<sub>3</sub>CN), and [(FeW<sub>5</sub>Br<sub>13</sub>)<sub>2</sub>O]<sup>4-</sup>, were revealed and characterized by single-crystal X-ray diffraction analysis. The redox properties of [FeW<sub>5</sub>Br<sub>14</sub>]<sup>2-</sup> were studied and compared with those of [W<sub>6</sub>Br<sub>14</sub>]<sup>2-</sup>. Density functional theory calculations demonstrated that the bonding between Fe and W atoms is fundamentally different from the bonding between 4d (Mo-Mo) or 5d (W-W) metals in isotypic {M<sub>6</sub>} clusters.

Inorganic ChemistryVol. 63(35)
Novosibirsk State University (RU), Boreskov Institute of Catalysis (RU), Siberian Branch of the Russian Academy of Sciences (RU), Nikolaev Institute of Inorganic Chemistry (RU), International Tomography Center (RU)
Ministry of Science and Higher Education of the Russian Federation
Openalex Percentile: Top 59%
Inorganic Chemistry and Materials
0.16
DOISourceOpenAlex
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