Geitner Felix S, Wallach Christoph, Fässler Thomas F
WACKER Institute for Silicon Chemistry and Department Chemie, Technische Universität München, Lichtenbergstraße 4, 85747, Garching b. München, Germany.
Department Chemie, Technische Universität München, Lichtenbergstraße 4, 85747, Garching b. München, Germany.
Chemistry. 2018 Mar 15;24(16):4103-4110. doi: 10.1002/chem.201705678. Epub 2018 Feb 16.
The reaction of [(Ge {Si(TMS) } PtBu )] with NHC CuCl yields [(Ge {Si(TMS) } )(tBu P)]Cu(NHC ) (1), which is a new derivative of the recently reported monomeric zwitterionic tetrel cluster compounds [(Ge {Si(TMS) } )(tBu P)]M(NHC ) (M: Cu, Ag, Au). By contrast, the reaction of the same anion [(Ge {Si(TMS) } PtBu )] with the more labile copper phosphine complex Cy PCuCl leads to the formation of [Ge {Si(TMS) } {(tBu) PCu} Ge {Si(TMS) } ] (2), which is a neutral dimeric twofold-bridged [Ge ] cluster compound, with the exo-bonded phosphine substituent being involved in the cluster bridging. In case of the presence of sterically more demanding phosphines in [Ge {Si(TMS) } PR ] [R: Mes (3) and NiPr (4)], reactions with NHC CuCl yielded the complexes NHC Cu[η -Ge {Si(TMS) } (PR )] [R: Mes (5) and NiPr (6)], comprising exclusively Cu-Ge bonds. Compounds 5 and 6 show varying reactivity in dependence of the identity of the phosphine group and represent the first examples of fourfold-substituted [Ge ] clusters with three different ligands bound to the [Ge ] cluster core. All compounds were characterized by H, C, P, and Si NMR spectroscopy. Additionally, compounds 3 and 4 were analyzed by ESI-MS, and the structures of compounds 1, 2, and 5 were characterized by single-crystal X-ray diffraction.
[(Ge{Si(TMS)}PtBu)]与NHC CuCl反应生成[(Ge{Si(TMS)})(tBuP)]Cu(NHC)(1)，它是最近报道的单体两性离子四元簇化合物[(Ge{Si(TMS)})(tBuP)]M(NHC)(M: Cu、Ag、Au)的新衍生物。相比之下，相同阴离子[(Ge{Si(TMS)}PtBu)]与更不稳定的铜膦配合物CyPCuCl反应生成Ge{Si(TMS)}{(tBu)PCu}Ge{Si(TMS)}，它是一种中性二聚双桥连[Ge]簇化合物，外部键合的膦取代基参与簇桥连。在[Ge{Si(TMS)}PR](R: Mes(3)和NiPr(4))中存在空间位阻更大的膦的情况下，与NHC CuCl反应生成配合物NHC Cu[η-Ge{Si(TMS)}(PR)](R: Mes(5)和NiPr(6))，仅包含Cu-Ge键。化合物5和6根据膦基团的不同表现出不同的反应性，并且代表了具有与[Ge]簇核心相连的三种不同配体的四元取代[Ge]簇的首例。所有化合物均通过1H、13C、31P和29Si NMR光谱进行表征。此外，化合物3和4通过ESI-MS进行分析，化合物1、2和5的结构通过单晶X射线衍射进行表征。
