Geitner Felix S, Fässler Thomas F
WACKER-Institute for Silicon Chemistry and Department of Chemistry, Technische Universität München, Lichtenbergstraße 4, 85747 Garching, Germany.
Chem Commun (Camb). 2017 Nov 30;53(96):12974-12977. doi: 10.1039/c7cc07995h.
The reaction of NHCCuCl with the silicide phases ASi (A: K, K/Rb, Rb) in NH(l) yields [NHCCu(η-Si)] (1) as only the third example of a substituted [Si] cluster. The corresponding salts A[A(2.2.2-crypt)][NHCCu(η-Si)]·26NH (A: K (1a), K/Rb (1b), Rb (1c)) crystallize isostructurally in the space group P1[combining macron] and have been characterized by single crystal structure determination. ESI-MS and NMR experiments reveal that the anion [NHCCu(η-Si)] can also be transferred to pyridine or acetonitrile solutions at low temperature. However, at room temperature dissociation under the release of the NHC ligand occurs. Variation of the NHC ligand in the [Cu-NHC]-substituted silicide clusters is possible, whereas the reactions of KSi with the corresponding NHCMCl (M: Ag, Au) complexes result in a partial oxidation of the silicide clusters, without attachment of [M-NHC], yielding [Si] species.
NHCCuCl与硅化物相ASi（A：K、K/Rb、Rb）在液氨（NH(l)）中的反应生成了[NHCCu(η-Si)]（1），这是取代[Si]簇的第三个例子。相应的盐A[A(2.2.2-穴醚)][NHCCu(η-Si)]·26NH（A：K（1a）、K/Rb（1b）、Rb（1c））在空间群P1[组合宏]中同构结晶，并通过单晶结构测定进行了表征。电喷雾电离质谱（ESI-MS）和核磁共振（NMR）实验表明，阴离子[NHCCu(η-Si)]在低温下也能转移到吡啶或乙腈溶液中。然而，在室温下会发生NHC配体释放下的解离。[Cu-NHC]取代的硅化物簇中的NHC配体可以变化，而KSi与相应的NHCMCl（M：Ag、Au）配合物的反应会导致硅化物簇的部分氧化，没有[M-NHC]的附着，生成[Si]物种。
