Ligand exchange reactions of [Rh(COD){η⁴-Ge₉(Hyp)₃}] with L-type nucleophiles such as PMe₃, PPh₃, IMe₄ (IMe₄ = 1,3,4,5-tetramethylimidazol-2-ylidene) or [W(Cp)₂H₂] result in the displacement of the COD ligand to afford clusters with coordinatively unsaturated trigonal pyramidal rhodium(I) centers [Rh(L){η³-Ge₉(Hyp)₃}]. These species can be readily protonated allowing access to cationic rhodium–hydride complexes, e.g. [RhH(PPh₃){η³-Ge₉(Hyp)₃}]⁺. These clusters act as catalysts in H/D exchange between H₂ and D₂ and alkene isomerisation, thereby illustrating that metal-functionalized Zintl clusters are active in both H–H and C–H bond activation processes. The mechanism of H/D exchange was probed using parahydrogen induced polarization experiments.

中文翻译：

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Zintl 簇支持低坐标 Rh(I) 中心，用于 H2 和 D2 之间的催化 H/D 交换

[Rh(COD){η ⁴ -Ge ₉ (Hyp) ₃ }] 与 L 型亲核试剂如 PMe ₃、PPh ₃、IMe ₄ (IMe ₄ = 1,3,4,5-四甲基咪唑- 2-亚叉基) 或 [W(Cp) ₂ H ₂ ] 导致 COD 配体的置换以提供具有配位不饱和三角锥体铑 ( I ) 中心 [Rh(L){η ³ -Ge ₉ (Hyp) ₃的簇}]。这些物质可以很容易地质子化，从而可以接触到阳离子铑-氢化物络合物，例如[RhH(PPh ₃ ){η ³-Ge ₉ (Hyp) ₃ }] ⁺ . _{这些簇在 H 2}和 D ₂之间的 H/D 交换和烯烃异构化中充当催化剂，从而说明金属官能化的 Zintl 簇在 H-H 和 C-H 键活化过程中均具有活性。使用对氢诱导极化实验探讨了H/D交换的机制。