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Bromination of Pyrazole and Pyrazolate Ligands in [Mo5S5(pz)4(pzH)5]Br2

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Abstract

The ligand environment of the \([\{\text{Mo}_{5}\text{S}_{5}^{\text{i}}(\text{pz})_{4}^{\text{i}}\}(\text{pzH})_{5}^{\text{t}}]\text{Br}_{2}\) cluster complex is modified by a reaction of the cluster with Br2 in N,N-dimethylformamide at room temperature, which results in bromination of all pyrazole and pyrazolate ligands at the fourth position and in bromide ligand substitution for apical pyrazole. The solvent effect on ligand bromination is considered. The \([\{\text{Mo}_{5}\text{S}_{5}^{\text{i}}(4\text{-Br-pz})_{4}^{\text{i}}\}(4\text{-Br-pzH})_{4}^{\text{bs}}\text{B}{{\text{r}}^{\text{a}}}]\text{Br}\cdot \text{E}{{\text{t}}_{2}}\text{O}\cdot \text{5DMF}\) cluster complex crystallizes in the tetragonal symmetry (space group P4/n) and forms infinite layers via hydrogen bonds between the terminal 4-bromopyrazole ligands and the bromine anion. The complex also demonstrates reversible one-electron reductions of the cluster core shifted relative to the initial compound by 30 mV and 90 mV towards larger potentials.

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Funding

The work was supported by the Russian Science Foundation (Grant No. 19-73-20109).

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Authors and Affiliations

  1. Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia

    I. V. Savina, A. A. Ivanov & M. A. Shestopalov

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  1. I. V. Savina
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  2. A. A. Ivanov
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  3. M. A. Shestopalov
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Correspondence to A. A. Ivanov.

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Russian Text © The Author(s), 2023, published in Zhurnal Strukturnoi Khimii, 2023, Vol. 64, No. 12, 122349.https://doi.org/10.26902/JSC_id122349

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Savina, I.V., Ivanov, A.A. & Shestopalov, M.A. Bromination of Pyrazole and Pyrazolate Ligands in [Mo5S5(pz)4(pzH)5]Br2. J Struct Chem 64, 2451–2460 (2023). https://doi.org/10.1134/S0022476623120168

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