Department of Chemistry, Technical University of Munich , Lichtenbergstraße 4, 85747 Garching, Germany.
WACKER Institute for Silicon Chemistry , Lichtenbergstraße 4, 85747 Garching, Germany.
J Am Chem Soc. 2017 Aug 30;139(34):11933-11940. doi: 10.1021/jacs.7b05834. Epub 2017 Aug 21.
Reactions of silylated clusters [Ge{Si(TMS)}] or [Ge{Si(TMS)}] with dialkylhalophosphines RPCl (Cy, Pr, Bu) at ambient temperature yield the first tetrel Zintl cluster compounds bearing phosphine moieties. Varying reactivity of the dialkylhalophosphines toward the silylated clusters is observed depending on the bulkiness of the phosphine's alkyl substituents and on the number of hypersilyl groups at the tetrel cluster. Reactions between phosphines with small cyclohexyl- (Cy) or isopropyl- (Pr) groups and the tris-silylated cluster [Ge{Si(TMS)}] yield the novel neutral cluster compounds [Ge{Si(TMS)}PR] (R: Cy (1), Pr (2)) with discrete Ge-P exo bonds. By contrast, the bulkier phosphine BuPCl does not react with [Ge{Si(TMS)}] due to steric crowding. However, the reaction with the bis-silylated cluster [Ge{Si(TMS)}] yields the novel cluster compound [Ge{Si(TMS)}PBu] (3). Subsequent reactions of compound 3 with NHCMCl (M: Cu, Ag, Au) yield the charge neutral zwitterionic compounds [(Ge{Si(TMS)})BuP]M(NHC) (M: Cu, Ag, Au) (4-6), in which compound 3 acts as a phosphine ligand bearing a bulky tetrel Zintl cluster moiety. Compounds 4-6 also represent the first uncharged examples for 3-fold substituted tetrel Zintl clusters.
硅烷化簇[Ge{Si(TMS)}]或[Ge{Si(TMS)}]与二烷基卤代膦RPCl（Cy、Pr、Bu）在环境温度下反应，生成了首例含有膦部分的四族 Zintl 簇化合物。二烷基卤代膦对硅烷化簇的反应性因膦的烷基取代基的体积和四族簇上的超硅烷基数目而异。具有较小环己基（Cy）或异丙基（Pr）基团的膦与三硅烷化簇[Ge{Si(TMS)}]之间的反应生成了新型中性簇化合物[Ge{Si(TMS)}PR]（R：Cy（1），Pr（2）），其中存在离散的 Ge-P 外向键。相比之下，由于空间位阻，较大的膦 BuPCl 与[Ge{Si(TMS)}]不反应。然而，与双硅烷化簇[Ge{Si(TMS)}]的反应生成了新型簇化合物[Ge{Si(TMS)}PBu]（3）。化合物 3 与 NHCMCl（M：Cu、Ag、Au）的后续反应生成了电荷中性的两性离子化合物[(Ge{Si(TMS)})BuP]M(NHC)（M：Cu、Ag、Au）（4-6），其中化合物 3 充当带有大体积四族 Zintl 簇部分的膦配体。化合物 4-6 也是首例未取代的三取代四族 Zintl 簇的例子。
