Low and medium oxidation state organometallic complexes with triseleno- and telluro-ether ligands have been prepared. Reaction of [M(COD)Cl]2 (M = Rh or Ir) with two molar equivalents of L3 (L3 = MeC(CH2ER)3, E = Se, R = Me; E = Te, R = Me or Ph) and two molar equivalents of NH4PF6 at room temperature in CH2Cl2 affords the species [M(COD)(L3)][PF6]. These complexes, which represent the first seleno- or telluro-ether complexes of RhI or IrI, have been characterised by analysis, IR and multinuclear NMR spectroscopy. The crystal structures of [Rh(COD)MeC(CH2SeMe)3}]PF6, [Ir(COD)MeC(CH2SeMe)3}]PF6, [Rh(COD)MeC(CH2TeMe)3}]PF6 and [Ir(COD)MeC(CH2TePh)3}]PF6 reveal distorted square pyramidal geometries. The rhodium(III) and iridium(III) complexes [M(C5Me5)(L3)][PF6]2 have been prepared via the reaction of [M(C5Me5)Cl2]2 with 2 mol equivalents of L3 and 4 of TlPF6 in refluxing MeOH. Comparisons of the spectroscopic and crystallographic data for the metal(I) complexes reveal superior σ donation by the ligand MeC(CH2TeMe)3 compared with its selenoether analogue. In contrast, the medium oxidation state metal(III) complexes show enhanced donation by the selenoether ligand. The reaction of the COD complexes with H2 is also described.
                                    我们制备了具有三
硒醚和三
碲醚
配体的低氧化态和中氧化态有机
金属配合物。室温下,[M(COD)Cl]2(M = Rh 或 Ir)与两摩尔当量的 L3(L3 = MeC(CH2ER)3,E = Se,R = Me;E = Te,R = Me 或 Ph)和两摩尔当量的 NH4PF6 在 
CH2Cl2 中反应,生成 [M(COD)(L3)][PF6]。这些络合物是 RhI 或 IrI 的首个
硒醚或
碲醚络合物,已通过分析、红外光谱和多核核磁共振光谱对其进行了表征。[Rh(COD)MeC(CH2SeMe)3}]PF6、[Ir(COD)MeC(CH2SeMe)3}]PF6、[Rh(COD)MeC(CH2TeMe)3}]PF6 和[Ir(COD)MeC(CH2TePh)3}]PF6 的晶体结构显示出扭曲的正方
金字塔几何结构。
铑(III)和
铱(III)配合物[M(C5Me5)(L3)][PF6]2 是通过[M(C5Me5)Cl2]2 与 2 摩尔当量的 L3 和 4 摩尔当量的 TlPF6 在回流的 MeOH 中反应制备的。对
金属(I)配合物的光谱和晶体学数据进行比较后发现,与
硒醚类似物相比,
配体 MeC(CH2TeMe)3 的σ捐赠效果更好。相反,中等氧化态的
金属(III)配合物则显示
硒醚
配体的捐献能力更强。此外,还介绍了 COD 复合物与 H2 的反应。