MesPX2/IsPX2 as Precursors for the Preparation of Phosphasilenes

Abstract

Abstract The one‐pot reaction of L1SiCl (L1=PhC(NtBu)2) with MesPX2/IsPX2 (X=Cl, Br; Is=2,4,6‐iPr3C6H2, Mes=2,4,6‐Me3C6H2) in the presence of KC8 yielded two phosphasilene compounds L1Si(Cl)=PIs (1) and L1Si(Cl)=PMes (2) with interesting Cl−Si=P characteristics. The introduction of Cl−Si=P moiety improved the reactivity of phosphasilene. Furthermore, phosphasilenes 1 and 2 with LSi as well as Si=P building units are sensitive to moisture with distinct differences. The hydrolysis of 2 resulted in two products [L1(PHMes)Si]2(μ‐O)2 (3) and L1Cl (4), respectively, due to the amount of water, while the hydrolysis of 1 afforded L1Cl (4). In addition to the silylene L1SiCl, different types of aluminum compounds were studied to react with IsPX2/MesPX2 in the presence of KC8 in THF at low temperature. However, we failed to isolate the desired compounds due to the formation of numerous by‐products. The one‐pot reaction of L1SiCl (L1=PhC(NtBu)2) with MesPX2/IsPX2 (X=Cl, Br; Is=2,4,6‐iPr3C6H2, Mes=2,4,6‐Me3C6H2) in the presence of KC8 yielded two phosphasilene compounds L1Si(Cl)=PIs and L1Si(Cl)=PMes with interesting Cl−Si=P characteristics. The phosphasilene compounds containing the Cl−Si=P moiety exhibit high reactivity and can participate in various reactions. image