TY - JOUR

T1 - Unusual Square Pyramidal Chalcogenide Mo5 Cluster with Bridging Pyrazolate-Ligands

AU - Savina, Iulia V

AU - Ivanov, Anton A

AU - Evtushok, Darya V

AU - Gayfulin, Yakov M

AU - Komarovskikh, Andrey Y

AU - Syrokvashin, Mikhail M

AU - Ivanova, Mariia N

AU - Asanov, Igor P

AU - Eltsov, Ilia V

AU - Kuratieva, Natalia V

AU - Mironov, Yuri V

AU - Shestopalov, Michael A

N1 - Funding: This work was funded by the Russian Science Foundation (No. 19-73-20109).

PY - 2023/2/8

Y1 - 2023/2/8

N2 - 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.

AB - 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.

KW - DFT calculations

KW - EPR

KW - NMR

KW - XPS

KW - cyclic voltammetry

KW - metal clusters

KW - molybdenum

UR - https://www.scopus.com/record/display.uri?eid=2-s2.0-85149053844&origin=inward&txGid=41f348d3f3b1a91207b029149c517c00

UR - https://www.mdpi.com/1422-0067/24/4/3440

UR - https://www.mendeley.com/catalogue/c9d4f95f-e450-35d0-be45-eaf692932fb2/

U2 - 10.3390/ijms24043440

DO - 10.3390/ijms24043440

M3 - Article

C2 - 36834850

VL - 24

JO - International Journal of Molecular Sciences

JF - International Journal of Molecular Sciences

SN - 1661-6596

IS - 4

M1 - 3440

ER -