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<p>The family of chalcogenide rhenium clusters is well represented in the literature by a series of compounds with different nuclearities, including heterometallic complexes. Here we report the synthesis and detailed characterization of new cyanide clusters [{Re<sub>8</sub>Se<sub>8</sub>(µ-O)<sub>3</sub>}(CN)<sub>18</sub>]<sup>8–</sup> and [{Re<sub>12</sub>S<sub>14</sub>}(CN)<sub>27</sub>]<sup>9–</sup>. Both compounds were obtained by reactions of ReI<sub>3</sub>, RuCl<sub>3</sub> and elemental selenium or sulfur with KCN at elevated temperatures, reflecting attempts to prepare heterometallic complexes with noble metals. The first cluster can be visualized as two fragments [{Re<sub>4</sub>Se<sub>4</sub>}(CN)<sub>9</sub>]<sup>–</sup> linked by three µ-O<sup>2–</sup> bridging ligands. The second one can be represented as three tetrahedral [{Re<sub>4</sub>S<sub>4</sub>}(CN)<sub>9</sub>]<sup>–</sup> fragments linked by two µ<sub>3</sub>-bridged sulfide ligands. Two of three {Re<sub>4</sub>S<sub>4</sub>} cores are additionally linked by direct Re–Re bond.</p>

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Synthesis of Two New Rhenium Clusters [{Re8Se8(µ-O)3}(CN)18]8– and [{Re12S14}(CN)27]9–

  • 期刊论文

  • 发表日期：

    2025年8月29日

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  • Aleksei S. Pronin,
  • Yakov M. Gaifulin,
  • Taisiya S. Sukhikh,
  • Vadim V. Yanshole,
  • Yuri V. Mironov

摘要

The family of chalcogenide rhenium clusters is well represented in the literature by a series of compounds with different nuclearities, including heterometallic complexes. Here we report the synthesis and detailed characterization of new cyanide clusters [{Re8Se8(µ-O)3}(CN)18]8– and [{Re12S14}(CN)27]9–. Both compounds were obtained by reactions of ReI3, RuCl3 and elemental selenium or sulfur with KCN at elevated temperatures, reflecting attempts to prepare heterometallic complexes with noble metals. The first cluster can be visualized as two fragments [{Re4Se4}(CN)9]– linked by three µ-O2– bridging ligands. The second one can be represented as three tetrahedral [{Re4S4}(CN)9]– fragments linked by two µ3-bridged sulfide ligands. Two of three {Re4S4} cores are additionally linked by direct Re–Re bond.