Exploring the Frontiers of Heterometallic Systems: the {FeW5} 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)2[FeW5Br14] (TBA = tetrabutylammonium), exhibits selective ligand substitution reactions at the iron site when exposed...

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Veröffentlicht in:Inorganic chemistry 2024-09, Vol.63 (35), p.16128-16133
Hauptverfasser: Kozyreva, Anastasia I., Yudin, Vasiliy N., Gaifulin, Yakov M., Ivanov, Anton A., Yanshole, Vadim V., Shestopalov, Michael A., Asanov, Igor P., Evtushok, Vasilii Yu, Evtushok, Darya V.
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Sprache:eng
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Zusammenfassung: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)2[FeW5Br14] (TBA = tetrabutylammonium), exhibits selective ligand substitution reactions at the iron site when exposed to various solvents. Several {FeW5}-type anions, namely, [FeW5Br14]2–, [FeW5Br13(L)]− (L = H2O, DMSO, CH3CN), and [(FeW5Br13)2O]4–, were revealed and characterized by single-crystal X-ray diffraction analysis. The redox properties of [FeW5Br14]2– were studied and compared with those of [W6Br14]2–. 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 {M6} clusters.
ISSN:0020-1669
1520-510X
1520-510X
DOI:10.1021/acs.inorgchem.4c02594