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.

中文翻译：

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[Mo5S5(pz)4(pzH)5]Br2 中吡唑和吡唑酯配体的溴化

摘要

\([\{\text{Mo}_{5}\text{S}_{5}^{\text{i}}(\text{pz})_{4}^{\ 的配体环境text{i}}\}(\text{pzH})_{5}^{\text{t}}]\text{Br}_{2}\)簇复合体通过簇与 Br 的反应进行修改₂在室温下，N,N-二甲基甲酰胺中，导致所有吡唑和吡唑酯配体在第四位发生溴化，并导致顶部吡唑被溴化物配体取代。考虑了溶剂对配体溴化的影响。\ ([\{\text{Mo}_{5}\text{S}_{5}^{\text{i}}(4\text{-Br-pz})_{4}^{\文本{i}}\}(4\文本{-Br-pzH})_{4}^{\文本{bs}}\文本{B}{{\文本{r}}^{\文本{a} }}]\text{Br}\cdot \text{E}{{\text{t}}_{2}}\text{O}\cdot \text{5DMF}\) 簇络合物以四方对称结晶 (空间群P 4/ n )并通过末端4-溴吡唑配体和溴阴离子之间的氢键形成无限层。该复合物还证明簇核的可逆单电子还原相对于初始化合物向更大电势移动了 30 mV 和 90 mV。