Unusual Square Pyramidal Chalcogenide Mo5 Cluster with Bridging Pyrazolate-Ligands

Unusual Square Pyramidal Chalcogenide Mo5 Cluster with Bridging Pyrazolate-Ligands

The family of chalcogenide molybdenum clusters is well presented in the literature by a series of compounds of nuclearity ranging from binuclear to multinuclear articulating octahedral fragments. Clusters actively studied in the last decades were shown to be promising as components of superconductin...

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Bibliographic Details
Published in:International journal of molecular sciences 2023-02, Vol.24 (4), p.3440
Main Authors: Savina, Iulia V., Ivanov, Anton A., Evtushok, Darya V., Gayfulin, Yakov M., Komarovskikh, Andrey Y., Syrokvashin, Mikhail M., Ivanova, Mariia N., Asanov, Igor P., Eltsov, Ilia V., Kuratieva, Natalia V., Mironov, Yuri V., Shestopalov, Michael A.
Format: Article
Language:eng
Subjects:
Chalcogenides
Clusters
Crystals
cyclic voltammetry
EPR
Hydrogen bonds
Ligands
Magnetic properties
metal clusters
Molybdenum
NMR
Oxidation
Pyrazole
Pyrazoles
Single crystals
Solvents
X-ray diffraction
XPS
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Summary:The family of chalcogenide molybdenum clusters is well presented in the literature by a series of compounds of nuclearity ranging from binuclear to multinuclear articulating octahedral fragments. Clusters actively studied in the last decades were shown to be promising as components of superconducting, magnetic, and catalytic systems. Here, we report the synthesis and detailed characterization of new and unusual representatives of chalcogenide clusters: square pyramidal complexes [{Mo5(μ3-Se)i4(μ4-Se)i(μ-pz)i4}(pzH)t5]1+/2+ (pzH = pyrazole, i = inner, t = terminal). Individually obtained oxidized (2+) and reduced (1+) forms have very close geometry (proven by single-crystal X-ray diffraction analysis) and are able to reversibly transform into each other, which was confirmed by cyclic voltammetry. Comprehensive characterization of the complexes, both in solid and in solution, confirms the different charge state of molybdenum in clusters (XPS), magnetic properties (EPR), and so on. DFT calculations complement the diverse study of new complexes, expanding the chemistry of molybdenum chalcogenide clusters.
ISSN:1422-0067
1661-6596
1422-0067