Geitner Felix S, Giebel Michael A, Pöthig Alexander, Fässler Thomas F
Wacker Institute for Silicon Chemistry and Department of Chemistry, Technische Universität München, Lichtenbergstraße 4, 85747 Garching, Germany.
Department of Chemistry, Technische Universität München, Lichtenbergstraße 4, 85747 Garching, Germany.
Molecules. 2017 Jul 19;22(7):1204. doi: 10.3390/molecules22071204.
We report on the synthesis of novel coinage metal NHC (-heterocyclic carbene) compounds of the germanium-rich metalloid clusters [Ge₉R₃] and [Ge₉R₂]² with R = Si(Pr)₃ and R = Si(TMS)₃. NHCCu{η³Ge₉R₃} with R = Si(Pr)₃ () represents a less bulky silyl group-substituted derivative of the known analogous compounds with R = Si(Bu)₃ or Si(TMS)₃. The coordination of the [NHCCu]⁺ moiety to the cluster unit occurs via one triangular face of the tri-capped trigonal prismatic [Ge₉] cluster. Furthermore, a series of novel cluster coinage metal NHC compounds of the type (NHC)₂{η³Ge₉R₂} (R = Si(TMS)₃ = Cu, Ag and Au; NHC = NHC or NHC) is presented. These novel compounds represent a new class of neutral dinuclear cluster coinage metal NHC compounds, which are obtained either by the stepwise reaction of a suspension of KGe with Si(TMS)₃Cl and the coinage metal carbene complexes NHCCl ( = Cu, Ag, Au), or via a homogenous reaction using the preformed bis-silylated cluster K₂[Ge₉(Si(TMS)₃)₂] and the corresponding NHCCl ( = Cu, Ag, Au) complex. The molecular structures of NHCCu{η³Ge₉(Si(Pr)₃)₃} () and (NHCCu)₂{η³-Ge₉(Si(TMS)₃)₂} () were determined by single crystal X-ray diffraction methods. In , the coordination of the [NHCCu]⁺ moieties to the cluster unit takes place via both open triangular faces of the [Ge₉] entity. Furthermore, all compounds were characterized by means of NMR spectroscopy (¹H, C, Si) and ESI-MS.
我们报道了富含锗的类金属簇合物[Ge₉R₃]和[Ge₉R₂]²（R = Si(Pr)₃和R = Si(TMS)₃）的新型铸币金属NHC（-杂环卡宾）化合物的合成。R = Si(Pr)₃的NHCCu{η³Ge₉R₃}（）代表了已知类似化合物（R = Si(Bu)₃或Si(TMS)₃）的一种体积较小的硅烷基取代衍生物。[NHCCu]⁺部分与簇单元的配位通过三帽三角棱柱形[Ge₉]簇的一个三角形面发生。此外，还展示了一系列新型的(NHC)₂{η³Ge₉R₂}类型的簇铸币金属NHC化合物（R = Si(TMS)₃， = Cu、Ag和Au；NHC = NHC或NHC）。这些新型化合物代表了一类新型的中性双核簇铸币金属NHC化合物，它们可以通过KGe悬浮液与Si(TMS)₃Cl和铸币金属卡宾配合物NHCCl（ = Cu、Ag、Au）的逐步反应获得，或者通过使用预先形成的双硅烷基化簇K₂[Ge₉(Si(TMS)₃)₂]和相应的NHCCl（ = Cu、Ag、Au）配合物的均相反应获得。通过单晶X射线衍射方法确定了NHCCu{η³Ge₉(Si(Pr)₃)₃}（）和(NHCCu)₂{η³-Ge₉(Si(TMS)₃)₂}（）的分子结构。在中，[NHCCu]⁺部分与簇单元的配位通过[Ge₉]实体的两个开放三角形面发生。此外，所有化合物都通过NMR光谱（¹H、C、Si）和ESI-MS进行了表征。
